1-Substituted aralkyl imidazoles and their use as fungicides

ABSTRACT

This disclosure describes novel aralkyl imidazoles, their acid addition salts, their metal complex salts and processes for their preparation. These compounds possess biological activity and in particular are useful as systemic protectant/eradicant fungicidal agents for controlling plant diseases caused by fungi and as plant growth regulators. The metal complex salts of these compounds are particularly useful in their ability to reduce undesirable plant growth regulatory activity and phytotoxicity while retaining their ability for controlling plant diseases caused by fungi.

SUMMARY OF THE INVENTION

This application is a continuation-in-part application of United Statesapplication Ser. No. 642,041, filed Dec. 8, 1975, now U.S. Pat. No.4,105,762 which is a continuation-in-part application of United Statesapplication Ser. No. 547,291, filed Feb. 5, 1975, now abandoned.

The 1-substituted aralkyl imidazoles of this invention possess eradicantfungicidal properties which are unique in that they killphytophathogenic fungi in infected plant tissues and therefore can beutilized after fungal infection has already occurred. The systemicproperties of these compounds are equally unique in that the compoundswill move both acropetally and basipetally in plant tissues.Furthermore, these compounds possess protectant properties againstphytopathogenic fungi when applied to the plants prior to infection.

This invention is concerned with the preparation and use of1-substituted aralkyl imidazoles of the formula: ##STR1## wherein Z is a(C₆ -C₁₄) aryl or a substituted (C₆ -C₁₄) aryl group; R¹ is a hydrogenatom, a (C₁ -C₁₀) alkyl group; a (C₂ -C₁₂) alkenyl group, a (C₇ -C₉)aralkyl or substituted (C₇ -C₉) aralkyl group; a phenyl or substitutedphenyl group, a (C₃ -C₇) cycloalkyl group, or a (C₅ -C₇) cycloalkenylgroup; R² is a (C₁ -C₁₀) alkyl group, a (C₂ -C₁₂) alkenyl group, a (C₇-C₉) aralkyl or substituted (C₇ -C₉) aralkyl group; a phenyl orsubstituted phenyl group, a (C₃ -C₇) cycloalkyl group, or a (C₅ -C₇)cycloalkenyl group; R¹ and R² when taken together form a (C₃ -C₈)cycloalkyl group; A and B are divalent (C₁ -C₅) alkylene groups; X is a(C₁ -C₄) alkyl group, a halogen atom or a nitro group; a is an integerfrom 0 to 3; n is the integer 0 or 1; n' is the integer 0 or 1; and thesum of n plus n' is equal to 1 or 2; or when Z is an unsubstitutedphenyl group, R¹ is a hydrogen atom, A is methylene, and n' is 0, thenR² is a (C₄ -C₁₀) alkyl group, a (C₂ -C₁₂) alkenyl group, a (C₇ -C₉)aralkyl or substituted (C₇ -C₉) aralkyl group, a phenyl or substitutedphenyl group, a (C₃ -C₇) cycloalkyl group or a (C₅ -C₇) cycloalkenylgroup.

A further embodiment of this invention is the metal salt complexes ofthe above 1-substituted aralkyl imidazoles having the formula: ##STR2##wherein Z, A, B, R¹, R², n, n', X and a are the same as above and M is ametal cation which can be selected from Groups IIA, IVA, VA, IB, IIB,VIB, VIIB and VIII of the Periodic Table. Y is a solubilizing anioncounterion and m is 1-4.

In the above description of Z the term "aryl" refers to a phenyl,naphthyl, biphenyl, acenaphthenyl, indanyl, indolyl, pyridyl, pyrimidyl,pyrryl, furyl or thienyl group preferably a phenyl group which can beunsubstituted or substituted with up to three substituents preferablytwo substituents selected from the group consisting of (C₁ -C₄) alkyl,methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro, amino, methylthioand trihalomethyl.

The terms "A" and "B" are divalent alkylene groups of from 1 to 5 carbonatoms which can be branched or straight chained.

The term "alkyl" in the description of R¹ and R² above refers to astraight or branched chain alkyl group of from 1 to 10 carbon atoms. Theterm "alkenyl" refers to a straight or branched chain alkenyl group offrom 2 to 12 carbon atoms. The term "cycloalkyl" refers to a cycloalkylgroup of from 3 to 7 carbon atoms and the term "cycloalkenyl" refers toa cycloalkenyl group of from 5 to 7 carbon atoms.

The term "aralkyl" refers to an aralkyl group of from 7 to 9 carbonatoms preferably benzyl or phenethyl which can be substituted with up totwo substituents selected from the group consisting of (C₁ -C₄) alkyl,methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro, amino, methylthioand trihalomethyl.

By the term substituted phenyl used in the definition of R¹ and R² ismeant a phenyl group which can be substituted with up to twosubstituents selected from the group consisting of (C₁ -C₄) alkyl,methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro, amino, methylthioand trihalomethyl.

The preferred compounds of this invention are those in which n' inFormulas I and II is one. The more preferred compounds of this inventionare those in which n' is one and n is zero. The most preferred compoundsof this invention are those in which n' is one, n is zero; R¹ is ahydrogen atom; a is zero; Z is a substituted phenyl group having up tothree substituents selected from the group consisting of (C₁ -C₄) alkyl,methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro, amino, methylthioand trihalomethyl, and R² is an alkyl group of from 4 to 10 carbonatoms, an alkenyl group of from 2 to 12 carbon atoms, an aralkyl groupof from 7 to 9 carbon atoms which can be substituted with up to twosubstituents selected from the group consisting of (C₁ -C₄) alkyl,methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro, amino, methylthioand trihalomethyl; a phenyl group which can be substituted with up totwo substituents selected from the group consisting of (C₁ -C₄) alkyl,methoxy, ethoxy, chloro, fluoro, bromo, iodo, nitro, amino, methylthioand trihalomethyl; a cycloalkyl group of from 3 to 7 carbon atoms or acycloalkenyl group of from 5 to 7 carbon atoms.

A preferred embodiment of this invention is a chemical compound selectedfrom the group consisting of an imidazole derivative having the formula##STR3## and the active acid addition salts thereof wherein Ar is amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl, and R is a member selected from thegroup consisting of (C₁ -C₁₀) alkyl, cycloalkyl, alkenyl, cycloalkenyland aralkyl, said aryl being a member selected from the group consistingof phenyl, mono-, di- and trihalophenyl, methylphenyl, ethylphenyl,methoxyphenyl, ethoxyphenyl, nitrophenyl and trihalomethylphenyl,provided that when Ar is unsubstituted phenyl then R is (C₄ -C₁₀) alkyl,cycloalkyl, alkenyl, cycloalkenyl and arylalkyl, said aryl being amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl.

Typical compounds encompassed by this invention include:

1-[β-(2,4-dichlorophenyl)hexyl]imidazole

1-[β-(2-chlorophenyl)hexyl]imidazole

1-[β-(4-bromophenyl)hexyl]imidazole

1-[β-(3-iodophenyl)hexyl]imidazole

1-[β-(2,6-dichlorophenyl)decyl]imidazole

1-[β-(2,4-dichlorophenyl)β-(p-chlorophenyl)ethyl]imidazole

1-[α-(2,4-dichlorobenzyl)pentyl]imidazole

1-[β-(2,4-dichlorobenzyl)hexyl]imidazole

1-[β-(2-methyl-4'-chlorophenyl)heptyl]imidazole

1-[β-(2,4-dichlorophenethyl)hexyl]imidazole

1-[β-(2,4-dichlorophenyl)nonyl]imidazole

1-[β-(2,4-dimethylthiophenyl)hexyl]imidazole

1-[β-(4-(nitrophenyl)hexyl]imidazole

1-[β-(3,4-dichlorophenyl)hexyl]imidazole

1-[β-(4-tolyl)hexyl]imidazole

1-[β-(4-anisyl)hexyl]imidazole

1-[β-(2,4-dichlorophenyl)-β-cyclopropyl ethyl]imidazole

1-[β-(2,4-dichlorophenyl)-β-cyclopentyl ethyl]imidazole

1-[β-(2,4-dichlorophenyl)-β-cycloheptyl ethyl]imidazole

1-[β,β-trimethylene-β-(2',4'-dichlorophenyl)ethyl]imidazole

1-[β,β-pentamethylene-β-(2',3'-dibromophenyl)ethyl]imidazole

1-[β,β-heptamethylene-β-(3',5'-difluorophenyl)ethyl]imidazole

The compounds of this invention can be prepared by standard methods ofsynthesis. Typical methods of preparation which can be utilized in thepreparation of these compounds include the following general syntheses,the temperatures given unless indicated otherwise are in degreescentigrade.

1-(β-substituted alkyl) imidazole

When the proper acetate derivative (III) is reacted with sodium hydridein tetrahydrofuran or glyme it forms the corresponding sodio salt (IV).The reaction of (IV) with an organic halide affords the ester (V).##STR4## These esters (V) are converted to the corresponding carbinolderivatives (VI) by a reduction with reagents such as lithium aluminumhydride (LiAlH₄) in ether or bis(2-methoxyethoxy) aluminum hydride inbenzene. The subsequent treatment of (VI) with methane sulfonyl chloridein the presence of triethyl amine in an aromatic hydrocarbon solventsuch as benzene or toluene provides the sulfonate (VII). Treatment of(VI) with thionyl chloride or phosphorus pentachloride in an aromatichydrocarbon such as benzene or toluene provides the chloride (VIIa). Thereaction of (VII) with excess of an imidazole or (VIIa) with the sodiumsalt of an imidazole either neat or in the presence of such solvents asbenzene, glyme, N,N-dimethylformamide, etc., gives the alkylatedimidazole products (VIII).

1-(α-substituted alkyl) imidazole

The 1-(α-substituted alkyl) imidazoles are synthesized by a differentroute. ##STR5##

The Grignard reagent (IX) is formed from the reaction of magnesium metalwith the appropriate organic chloride in ether. This reagent (IX)subsequently reacted with the desired aldehyde to provide the carbinolderivative (X). The formation of the sulfonate or chloride followed byits reaction with an imidazole or its sodio salt is carried out by thepreviously described route to give the product (XI).

Methylene Chain Extension-Malonate Route

A malonate synthesis is utilized to provide the starting materials forsome other closely related analogues where the methylene chain isextended. ##STR6## The reaction of an alkyl halide (XII) with sodioethyl malonate in a solvent such as THF or glyme gives the substitutedmalonate (XIII). A further reaction of (XIII) with first sodium hydridein THF followed by the addition of the appropriate organic halideaffords the disubstituted ester (XIV). A basic hydrolysis of (XIV) and asubsequent acidification and decarboxylation gives the mono acid (XV).The reduction of (XV) with LiAlH₄ gives the corresponding carbinolderivative (XVI). The alkylated imidazole product (XVII) is then formedby the usual route.

Methylene Chain Extension

The methylene chain can be extended from the methane sulfonate (VII) viathe preparation of the nitrile (XVIII). ##STR7##

This sulfonate (VII) in DMF is treated with sodium cyanide in DMF togive the nitrile derivative (XVIII). The hydrolysis of (XVIII) inboiling 50% sulfuric acid provides the acid (XIX) which is subsequentlyreduced with LiAlH₄ to provide the alcohol (XX). The imidazolederivative is then formed via the sulfonate in the usual way or thesulfonate can be recycled through the process for further chainextension.

Phenyl Analogues

The synthesis of the phenyl substituted analogue involves a Darzen'sreaction. A substituted benzophenone is reacted with ethyl chloroacetatein the presence of sodium hydride to give the glycidic ester (XXI).##STR8## A hydrolysis and a subsequent decarboxylation of (XXI) givesthe diaryl acetaldehyde (XXII). This aldehyde (XXII) is reduced to thecorresponding alcohol (XXIII) by LiAlH₄, and it is then converted to thealkylated imidazole product (XXIV) by the usual route.

αβ-Disubstituted alkylimidazole

The Friedel-Craft acylation of a substituted aromatic hydrocarbon withan acyl halide in the presence of aluminum chloride either neat or witha halogenated hydrocarbon provides the desired product (XXV). ##STR9##Treatment of (XXV) with an excess of ethyl chloroacetate and sodiumhydride gives the glycidic ester (XXVI) which upon saponification withbase and hydrolysis with hot mineral acid followed by decarboxylationgives the aldehyde (XXVII). A Grignard Reaction with an alkyl or arylmagnesium halide yields the alcohol (XXVIII). The formation of thesulfonate followed by its reaction with an imidazole as previouslydescribed gives the product XXIX.

β,β-disubstituted alkyl imidazole

When the appropriate sodio alkyl acetate derivative (XXX) prepared aspreviously described is reacted at elevated temperatures in a solventsuch as ether, tetrahydrofuran or dimethylformamide with an iodoalkanethe desired trisubstituted acetate (XXXI) is obtained. ##STR10##Reduction of (XXXI) with LiAlH₄ in anhydrous ether gives the alcohol(XXXII). Formation of the sulfonate followed by the imidazole reactionas previously described gives the desired product (XXXIII).

Alternate Routes to Phenyl Analogues

The reduction of a substituted phenylacetic acid (XXXIV) with LiAlH₄ intetrahydrofuran gives the alcohol (XXXV). ##STR11## Formation of thesulfonate by reaction with an imidazole gives the desired product(XXXVI).

1-(β-substituted diarylalkyl) imidazole

The reaction of chloroacetaldehyde diethylacetal with a substitutedaromatic hydrocarbon in the presence of sulfuric acid at roomtemperature gives the substituted arylethylchloride (XXXVII). Thereaction of (XXXVII) with the sodium salt of an imidazole as previouslydescribed affords the product (XXXVIII). ##STR12##

1-[ε-(substituted aryl) hexyl]imidazole

When a substituted aromatic hydrocarbon is treated with 1,2-epoxyhexanein the presence of aluminum chloride the rearranged hexanol (XXXIX) isobtained. ##STR13##

Formation of the methane sulfonate followed by the reaction with animidazole gives the product (XL).

When a benzene substituted with electron donating groups is treated with1,2-epoxyhexane in the presence of stannic chloride the hexanol (XLI) isobtained. ##STR14##

The imidazole derivative is formed via the above route from the methanesulfonate.

1-[β-(alkylthio or alkylsulfonyl substituted phenyl) alkyl]imidazoles

The alkylthio and alkylsulfonyl derivatives are prepared from thealdehyde (XLII). ##STR15## The aldehyde (XLII) is reduced to the alcohol(XLIII) with LiAlH₄. The alcohol (XLIII) is reacted with methanesulfonyl chloride in the presence of triethylamine to form the sulfonate(XLIV). Treatment of the methane sulfonate (XLIV) with sodium cyanidegives the benzyl nitrile derivative (XLV). Alkylation of the nitrile(XLV) via NaH metallation followed by treatment with alkylhalide givesthe α-alkyl benzyl nitrile derivative (XLVI). Hydrolysis of the nitrile(XLVI) with sulfuric acid in an alcoholic solvent gives the α-alkylphenylacetic acid ester (XLVII) which upon reduction with LiAlH₄ givesthe phenethyl alcohol (XLVIII). The imidazole product is formed via themethane sulfonate as shown above. When the imidazole (XLIX) is oxidizewith hydrogen peroxide in acetic acid the alkylsulfonyl (L) is formed.##STR16##

1-[β-(nitro substituted phenyl) alkyl]imidazole

The nitro substituted phenyl derivatives (LII) are formed by nitrationof the unsubstituted or substituted analogs (LI). ##STR17##

1-[β-(amino substituted phenyl) alkyl]imidazole

The amino substituted phenyl derivatives (LIII) are formed by reductionof the nitro substituted phenyl derivative. ##STR18##

Substituted imidazole derivatives

The analogs in which the imidazole rings itself is substituted (LV) areprepared by reacting the appropriate methane sulfonate (LIV) with eitheran excess of the substituted imidazole or the sodium salt of theimidazole. ##STR19##

The salts of aralkyl imidazole derivatives are prepared by treating anether solution of the imidazole (LVI) with an equivalent amount of thedesired inorganic or organic acid dissolved in ether or alcohol followedby filtration or concentration then filtration to give the desired salt.##STR20##

The metal complex salts of the aralkyl imidazole derivatives (LVIII) areprepared by the treatment of an alcoholic or aqueous solution of theimidazole (LVI) with a metal salt at temperatures from about 15° C. toabout 60° C.

The following examples are provided merely to illustrate the methods ofpreparation of the 1-substituted imidazoles and their metal complexsalts. These examples are not to be considered in any ways aslimitations of the scope of this invention.

EXAMPLE 1 1-[β-(2,4-dichlorophenyl) hexyl]imidazole 1.ethyl-β-(2,4-dichlorophenyl) hexanoate

To 58.6 g (1.22 mole) of 50% sodium hydride in 1 liter of anhydroustetrahydrofuran (THF) is added at 40°, 50.0 g (0.215 mole) ofethyl-2,4-dichlorophenyl acetate, and the mixture is stirred for 10 min.When the evolution of H₂ gas begins the temperature of the reaction islowered to 10°, and 200.0 g (0.858 mole) of additional ester is addeddropwise. When this addition is complete, the reaction is allowed tostir and to slowly warm up to ambient temperature. The reaction is thenheated at 40° for 1 hour and then it is cooled to ambient temperature.To the mixture is added at 20°, 198.0 g (1.076 mole) of 1-iodobutane,and when this addition is complete, the reaction is stirred at 40° for16 hours. The mixture is cooled, stripped down in volume, and pouredinto 1.5 liters of water. The insoluble oil is separated, and theaqueous layer is extracted with ether. The extract is combined with theoil. The ether solution is washed with 100 ml. of dilute hydrochloricacid, 100 ml. of sodium bicarbonate and finally 100 ml. of water. Thesolution is dried and concentrated to give 324.3 g. of crude product.Distillation of the product gives 223.0 g. (72%) of pure ester(115°-20°/0.25 mm). The material is identified by ir and its purity isdetermined by glc.

2. 2-(2,4-dichlorophenyl) hexan-1-ol

To 11.7 g. (0.308 mole) of lithium aluminum hydride in one liter ofanhydrous ether at 5°-10° is slowly added 140.0 g. (0.486 mole) of theprepared ethyl-β-(2,4-dichlorophenyl) hexanoate. When the addition iscomplete, the reaction is allowed to stir and slowly warm to ambienttemperature. The slurry is slowly added to iced water as H₂ gasvigorously evolves. When this addition is complete, the mixture is madeacidic with concentrated hydrochloric acid. The organic layer whichforms is separated, and the aqueous layer is extracted with ether. Thisextract is combined with the organic phase, and the solution is washedwith water and then with dilute sodium bicarbonate solution. Afterdrying over anhydrous magnesium sulfate, the ether solution isconcentrated and distilled (118°-23°/0.2 mm) to give 110.8 g. (92%) ofproduct.

3. 2-(2,4-dichlorophenyl) hexyl methane sulfonate

To 24.7 g. (0.1 mole) of the 2-(2,4-dichlorophenyl) hexan-2-ol and 13.8g. (0.12 mole) of methane sulfonyl chloride in 200 ml. of benzene at 10°is slowly added 14.2 g. (0.14 mole) of triethylamine. When the additionis complete, the reaction is stirred, and allowed to come up to ambienttemperature over a 30 minute period. The reaction slurry is then heatedto reflux for 30 minutes, cooled and poured into water. The organicsolution is washed with dilute hydrochloric acid then with water andfinally with dilute sodium bicarbonate solution. After drying overanhydrous magnesium sulfate, the benzene is stripped off to yield 31.8g. (98%) of the crude product. This material is identified by ir andnmr. The purity is determined by glc.

4. Imidazole Reaction

To 27.2 g. (0.4 mole) of imidazole at 95° is added 31.8 g (0.098 mole)of the 2-(2,4-dichlorophenyl) hexyl methane sulfonate, and the materialsare stirred at 95° for 16 hours. At the end of this period the reactionis cooled, and poured into 500 ml. of water. After stirring for one hourthe organic material is separate, and aqueous layer is extracted withether. The ether is combined with the organic phase, and after a waterwash is dried and concentrated to give 24.4 g. (88%) of product. Theimidazole product is identified by ir, nmr, and elemental analysis. Itspurity of greater than 95% is determine by glc.

EXAMPLE 2 1-[β-(2,4-dichlorophenyl) hexyl]-imidazole hydrochloride

In 30.0 g (0.101 mole) of 1-[β-(2,4-dichlorophenyl)hexyl]imidazoledissolved in 200 ml of ether is bubbled dry hydrogen chloride gas untilthe mixture is acidic to litmus. A colorless solid forms which isseparated by filtration to give 24.5 g. of the hydrochloride salt whichis identified by nmr.

EXAMPLE 3 1-[β-(2,4-dichlorophenyl) hexyl]imidazole zinc chloride MethodA

To a solution of 2.0 g (0.0067 mole) of1-[β-(2,4-dichlorophenyl)hexyl]imidazole in 10 ml of absolute ethanol isadded dropwise a solution of 0.46 g (0.0036 mole) of zinc chloride in 30ml of absolute ethanol. The reaction mixture is stirred at roomtemperature for 10 minutes and the solvent is removed under vacuum. Awhite glass-like solid is isolated as the product and is identified bynmr.

Method B

1-[β-(2,4-dichlorophenyl) hexyl]imidazole 2.0 g (0.0067 mole) and zincchloride 0.92 g (0.0067 mole) are mixed in an acetone: methanol: water(1:1:2) solvent system, 40 ml. This preparation is immediately appliedto plant foilage.

EXAMPLE 4 1-[β-2,4-dichlorophenyl) hexyl]imidazole oxalate

To a solution of 4 g (0.0135 mole) of 1-[β-(2,4-dichlorophenyl)hexyl]imidazole in ether is added dropwise a solution of 1.7 g (0.0135mole) of oxalic acid dissolved in 10 ml of methanol. A white precipitateforms immediately. The precipitate is collected by filtration and driedunder vacuum to give 3.37 g of a solid, m.p. 126°-128°.

EXAMPLE 26 1-[β-p-methylthiophenyl)hexyl]imidazole 1. p-Methylthiophenylmethanol

To 19.8 g (0.521 mole) of lithium aluminum hydride (LiAlH₄) in 750 ml ofanhydrous ether is slowly added 98 g. (0.64 mole) of p-methylmercaptobenzaldehyde in 250 ml of anhydrous ether at less than 10° C.When the addition is complete the reaction is stirred for 0.5 hour at10° C. and then the reaction is stopped by slowly adding 100 ml ofacetone to remove unreacted LiAlH₄.

To this mixture is added 500 ml of water and the reaction is made acidicby the addition of conc. hydrochloric acid. The ether layer isseparated, dried over anhydrous magnesium sulfate, and concentrated togive 89.6 g of the crude product. This residue is crystallized fromether-hexane to give 75.8 g, mp 38°-40° (76% yield).

2. p-Methylthiophenyl acetonitrile

To 73.0 g (0.47 mole) of p-methylthiophenyl methanol and 59.6 g (0.52mole) of methane sulfonyl chloride in 250 ml of benzene is slowly added59.6 g (0.59 mole) of triethylamine over a period of one hour at lessthan 15° C. When the addition is complete, the reaction is stirred forone hour and allowed to warm up to ambient temperature.

The reaction mixture is combined with 400 ml of dilute hydrochloricacid. The benzene layer is separated, washed with 250 ml of H₂ O, driedand concentrated to give 74.7 g of the crude mesylate product.

This residue is added to 25.5 g (0.52 mole) of sodium cyanide in 300 mlof dimethyl sulfoxide, and allowed to stir for one hour. The reaction ispoured into iced water and the yellow tinted solid which forms isfiltered and recrystallized from benzene-hexane to give 60.8 g (79%) ofthe product, mp 44°-5°.

3. 2-(p-Methylthiophenyl)hexanenitrile

To 12.5 g (0.25 mole) of 50% sodium hydride in 300 ml of anhydrous,distilled tetrahydrofurane is added 60.0 g (0.258 mole) of thep-methylthiophenyl acetonitrile over a period of one hour. The reactionmixture is allowed to stir for one hour then 48.8 g (0.265 mole) of1-iodobutane is slowly added. When the addition is complete, thereaction is stirred for two hours. The mixture is combined with 500 mlof water and the organic phase is separated, washed with water andconcentrated to give 80.1 g of crude product. Upon distillation 65.7 g(85%) of the product is isolated (126°-30°/0.01 mm.).

The imidazole derivative is then prepared by the method of Example 68parts 2, 3, 4 and 5.

EXAMPLE 27 1-[β-(p-methylsulfonylphenyl)hexyl]imidazole

To 7.0 g (0.021 mole) of 1-[β-(p-methylthiophenyl)hexyl]imidazole nitricacid salt in 75 ml of glacial acetic acid is added dropwise at less than10°, 8.0 g (0.083 mole) of 35% hydrogen peroxide. When the addition iscomplete, the reaction is stirred for one hour heated on a steambath fora second hour and then poured into iced water. The solution is madebasic to litmus with sodium hydroxide and the product is extracted outwith ether.

The ether extract is treated with nitric acid and the salt settles outan oil. This material is treated with aqueous sodium hydroxide to givethe product. An extraction with ether and concentration of thatextraction gives 2.1 g (25%) of the methylsulfonyl product.

EXAMPLE 29 1-[β-(p-nitrophenyl)hexyl]imidazole

To a mixture of 20 ml of nitric acid and 10 ml of sulfuric acid at 5° isslowly added 10.0 g (0.044 mole) of 1-[β-phenylhexyl]imidazole in 10 mlof sulfuric acid. As soon as the addition is complete, the reaction ispoured into iced water and the oil product settles out. The acidicsolution is decanted and the remaining oil is washed with water, andthen made basic with dilute sodium hydroxide. The product is extractedout with ether, dried and treated with nitric acid to precipitate thesalt. The salt is recrystallized from acetoneether to give 4.8 g mp.98°-100°. Treatment of the salt with dilute sodium hydroxide gives thefree base product.

EXAMPLE 30 1-[β-(p-aminophenyl)hexyl]imidazole

To 5.0 g [0.0183 mole) of 1-[β-(p-nitrophenyl)hexyl]imidazole in 50 mlof methanol is added 2.0 g of conc. hydrochloric acid. The solution isheated to reflux and 4 one gram portions of iron filings are added atfive min. intervals. When the additions are complete, the reactionslurry is stirred at reflux for 14 hours. The reaction is cooled, andthen poured into water. The organic material is extracted out withtoluene, dried and concentrated to give 4.5 g of the crude product.

The oil is dissolved in ether, and the solution is treated with nitricacid. The salt settles out as an oil. The oil is treated with dilutesodium hydroxide, extracted with ether, dried and concentrated to give3.5 g of the imidazole product.

EXAMPLE 31 1-[β-(2,4-dichloro-5-nitrophenyl)hexyl]imidazole

To a solution of 40 ml of nitric acid and 10 ml of sulfuric acid, 14.8 g(0.0498 mole) of 1-[β-(2,4-dichlorophenyl)hexyl]imidazole in 30 ml ofsulfuric acid is added at less than 5°. The reaction is stirred for 1/2hour and then it is poured into acid water. The oily solid whichseparates is isolated by decanting off the dilute acid solution. Theresidue is washed and then treated with ammonium hydroxide solution.

The organic product is extracted out with ether, and the extract isdried and treated with dry hydrogen chloride. The hydrochloride saltprecipitates out and is filtered to give 9.4 g of the crude product. Arecrystallization of 2.7 g of this material from methanol gives 1.8 g ofthe purified hydrochloride salt, mp 99°-100°.

EXAMPLE 46 1-[β-(2,4-dimethylphenylphenyl)hexyl]imidazole 1.2-(2,4-dimethylphenyl)hexan-1-ol

To a stirred, 0° C. mixture of m-xylene 173 g (1.63 mole) and anhydrousstannic chloride 78.0 g (0.30 mole) which is constantly swept withnitrogen, is added dropwise, 1,2-epoxyhexane, 30.0 g (0.30 mole) in 50 gm-xylene. The exothermic temperature is maintained at 3° C. by the rateof addition. After the addition is completed, the reaction which nowcontains 223 g (2.0 mole) m-xylene is stirred for 30 minutes at 0° C.then poured into iced concentrated hydrochloric acid. The aqueous andorganic layers are separated. After extracting the aqueous portion withethyl ether, this organic layer is combined with the previous organicfraction. This combined organic material is washed successively withwater, sodium bicarbonate and again water. The dried organic solventmixture of ethyl ether and excess unreacted m-xylene is then removed onrotary evaporator. The concentrated residue is fractionally distilled invacuo. The third fraction, 112° C./0.5 mm, is shown to be the desiredproduct by spectral and analytical data. The yield is 35.6 g (57.6%theory).

2. 1-[β-(2,4-dimethylphenyl)hexyl]imidazole

The imidazole is formed from the alcohol by the method of Example 1parts 3 and 4.

EXAMPLE 62 1-[α-(2,4-dimethoxyphenyl)hexyl]imidazole 1.2-(2,4-dimethoxyphenyl)hexan-1-ol

To a stirred, 5° C. mixture of m-dimethoxybenzene 27.6 g (0.20 mole),anhydrous stannic chloride 52.1 g (0.20 mole) and 200 ml of methylenechloride which is constantly swept with nitrogen, is added dropwise,1,2-epoxyhexane, 20.0 g (0.20 mole) in 50 ml of methylene chloride. Theexothermic reaction temperature is maintained at 3° C. by the rate ofaddition. After the addition is complete, the reaction is stirred at 5°C. for 30 minutes, at which time it is poured into iced concentratedhydrochloric acid. The layers are separated and the aqueous layer isextracted with methylene chloride. The combined organic layers arewashed with water followed by 5% sodium bicarbonate solution and finallywater. The last water wash is neutral to pH paper. The methylenechloride solvent is removed on a rotary evaporator at 40° C. bathtemperature. This residue is then fractionally distilled in vacuo. Thethird fraction, 140°-142° C./0.2 mm, is shown by nmr and ir to be thedesired product. The yield is 25.32 g (55%, theory).

2. 1-[α-(2,4-dimethoxyphenyl)hexyl]imidazole

The above alcohol forms the methane sulfonate via the method of Example1 part 3. However, upon reacting the methane sulfonate with imidazole bythe method of Example 1 part 4, a rearrangement takes place and theα-substituted product is obtained which is identified by ir and nmr.

EXAMPLE 66 1-[α-(2,4-dichlorobenzyl)pentyl]imidazole 1.α-(2,4-dichlorobenzyl)pentan-1-ol

To 7.5 g (0.384 mole) of magnesium turnings in 150 ml of ether is addeda 10.0 g (0.051 mole) portion of α,2,4-trichlorotoluene and a fewcrystals of iodine. When the iodine color has dissipated, the reactionis warmed to reflux, and 58.0 g (0.297 mole) of additionalα,2,4-trichlorotoluene in 50 ml of ether is added at such a rate thatthe refluxing is maintained. When the addition is complete, the reactionis stirred at reflux for 2 hours and cooled. To this reaction mixture isadded 17.0 g (0.197 mole) of valeraldehyde, and the reaction is heatedagain at reflux for 2 hours. The reaction is cooled and poured into icecold dilute hydrochloric acid, and the organic phase is separated. Theaqueous solution is extracted with ether, and the extract is combinedwith the organic phase. After a water wash, the organic solution isdried over anhydrous magnesium sulfate and stripped of solvent to give57.2 g of crude product. A distillation provides 11.3 g (23%) of theproduct. Purity is determined by glc.

2. 1-(2,4-dichlorobenzyl)pentyl methane sulfonate

The methane sulfonate is prepared according to the method of Example 1part 3, is identified by ir, and its purity determined by glc.

3. 1-[α-(2,4-dichlorobenzyl)pentyl]imidazole

The imidazole is prepared according to the method of Example 1 part 4,is identified by ir, nmr and elemental analysis and its purity ofgreater than 95% determined by glc.

EXAMPLE 67 1-[β-(2,4-dichlorobenzyl)hexyl]imidazole 1. ethylα-(2,4-dichlorobenzyl)malonate

To 4.6 g (0.095 mole) of 50% NaH in 250 ml of anhydrous THF is addedwith stirring 16.0 g (0.1 mole) of ethylmalonate, and the reactionslurry is allowed to stir for one hour, and then heated at reflux forthree hours. The reaction is cooled, and to it is added 17.5 g (0.09mole) α,2,4-trichlorotoluene. The resulting reaction slurry is heated toreflux for 16 hours. The reaction is cooled, and the THF is strippedoff. The concentrate is stirred with water, and the ester product isextracted out with ether. The ether solution is washed with water, driedover anhydrous magnesium sulfate and concentrated to give the crudeproduct. The residue is heated up to 110° under 0.1 mm pressure, and theexcess ethyl malonate is distilled off leaving 27.1 g (94%) of theproduct. The purity of the material is greater than 95% by glc.

2. ethyl,α-butyl-α-(2,4-dichlorobenzyl) malonate

To 6.7 g (0.14 mole) of 50% sodium hydride in 500 ml of anhydrous THF isadded at reflux, 44.2 g (0.139 mole) of the ethyl,α-(2,4-dichlorobenzyl) malonate, and the resulting slurry is stirred atreflux temperature for 16 hours. The reaction is cooled, and 26.6 g(0.14 mole) of 1-iodobutane is added. This mixture is heated, withstirring, at reflux for 6 hours.

The solvent is stripped off, and the concentrate is stirred with 500 mlof water. The product which separates is extracted out with ether andthe ether is washed twice with 100 ml of water. After drying overanhydrous magnesium sulfate, the ether is stripped to yield 60 g (>100%)of the crude product. By glc this sample is 95% pure.

3. α-(2,4-dichlorobenzyl)hexanoic acid

To 45.0 g (0.40 mole) of 50% potassium hydroxide is added 52.4 g (0.14mole) of the ethyl α-butyl-α-(2,4-dichlorobenzyl) malonate, and themixture is stirred at reflux for 16 hours. The reaction is cooled, andwashed twice with 75 ml of benzene. The aqueous solution is treated withconcentrated hydrochloric acid, and the malonic acid derivative settlesout. The oil is separated, and the aqueous solution is extracted withxylene. The extract is combined with the oil phase, dried over anhydrousmagnesium sulfate and heated up to reflux. After two hours, the xyleneis distilled off until the pot temperature reaches 180°. The reaction iscooled to give 46.0 g of crude product.

4. 2-(2,4-dichlorobenzyl) hexane-1-ol

To 9.4 g (0.248 mole) of lithium aluminum hydride in 600 ml of THF isslowly added, at less than 10°; 46.0 g of the crudeα-(2,4-dichlorobenzyl) hexanoic acid. The reaction is allowed to stir,and slowly warm up to ambient temperature. After 2 hours, the slurry isheated to reflux and held there for 16 hours. At the end of this period,the reaction is cooled and carefully poured into ice water to decomposethe excess LiAlH₄. The mixture is then made acidic by treatment withconcentrated hydrochloric acid. The ether solution is separated, and theaqueous phase is extracted three times with 200 ml of ether. Theextracts and the ether solution are combined and washed with 100 ml ofdilute sodium bicarbonate solution and then with 100 ml of water. Thesolution is dried over anhydrous magnesium sulfate and the ether isstripped off to give 35.9 g of the crude alcohol product. Distillation(86.8°/0.15 mm) provides 34.2 g (93%) of pure alcohol. The material isidentified by ir and its purity is determined by glc.

5. 2-(2,4-dichlorobenzyl) hexyl methane sulfonate

The methane sulfonate is prepared according to the method of Example 1part 3, the product is identified by ir and its purity determined byglc.

6. 1-[β-(2,4-dichlorobenzyl) hexyl]imidazole

The imidazole is prepared according to the method of Example 1 part 4,the product is identified by ir, nmr and elemental analysis and itspurity determined to be greater than 95% by glc.

EXAMPLE 68 1-[α-(2,4-dichlorophenyl) heptyl]imidazole 1.2-(2,4-dichlorophenyl) hexyl cyanide

To a suspension of 11.3 g (0.23 mole) of sodium cyanide in 100 ml of drydimethyl formamide (DMF) is added dropwise a solution of 50 g (0.154mole) of 2-(2,4-dichlorophenyl)-hexylmethane sulfonate in 50 ml of DMF.The reaction mixture is stirred at 70° overnight. It is then poured into500 ml of water and extracted with ether. The combined ether extractsare washed with water, then saturated saline solution and finally driedover magnesium sulfate. Solvent is evaporated under reduced pressure togive 37 g of crude product which is further purified by vacuumdistillation (107.5°-110°/0.05 mm) to give 33.9 g (86%) of expectedproduct.

2. 2-(2,4-dichlorophenyl) heptanoic acid

A mixture of 15 g (0.0596 mole) of 2-(2,4-dichlorophenyl) hexyl cyanideand 100 ml of 50% sulfuric acid is heated at 110° overnight. Thereaction mixture is cooled and diluted with 500 ml of water. Thisaqueous portion is extracted with ether and the combined ether extractsare dried over magnesium sulfate. Solvent is removed under reducedpressure to give 15.02 g (93.7%) of a white solid, mp 65°-68°.

3. 3-(2,4-dichlorophenyl)-heptan-1-ol

To a suspension of 2.07 g (0.0545 mole) of lithium aluminum hydride in100 ml of ether is added dropwise a solution of 15 g (0.054 mole) of2-(2,4-dichlorophenyl) heptanoic acid in 50 ml of ether. The resultingmixture is stirred at room temperature for 3 hours. The excess lithiumaluminum hydride is decomposed carefully with 100 ml of saturatedammonium chloride solution followed by 100 ml of dilute sulfuric acidsolution. The ether layer is separated from the aqueous layer and theaqueous layer is again extracted with ether. The combined ether layersare washed with 10% sulfuric acid, water, saturated sodium bicarbonatesolution, saturated saline solution and dried over magnesium sulfate.Solvent is evaporated under reduced pressure to give 12 g of an oilwhich is further purified by vacuum distillation (120°-125°/0.1 mm) togive 10.2 g (72%) of desired product.

4. 3-(2,4-dichlorophenyl)heptyl methane sulfonate

To 10.2 g (0.039 mole) of the 3-(2,4-dichlorophenyl) heptan-1-ol and 4.8g (0.042 mole) of methane sulfonyl chloride in 100 ml of benzene at 10°is slowly added 4.4 g (0.043 mole) of triethylamine. When the additionis complete, the reaction is stirred and allowed to come up to ambienttemperature over a 30 minute period. The reaction slurry is then heatedto reflux for 30 minutes, cooled and poured into water. The organicsolution is washed with dilute hydrochloric acid, then with water andfinally with dilute sodium bicarbonate solution. After drying overanhydrous magnesium sulfate, the benzene is stripped off to give 10.6 gof crude sulfonate product.

5. 1-[δ-(2,4-dichlorophenyl) heptyl imidazole

To 10.6 g (0.160 mole) of imidazole at 95° is added 10.9 g (0.042 mole)of the crude 8-(2',4'-dichlorophenyl) heptyl methane sulfonate. Thematerials are stirred at 95° for 16 hours, cooled and poured into 500 mlof water. After stirring for 1 hr., the organic material is separatedand the aqueous layer is extracted with ether. The ether is combinedwith the organic phase, and after a water wash, it is dried andconcentrated to give 10.6 g of the crude product.

EXAMPLE 69 1-[β-(2,4-dichlorophenyl) phenethyl]imidazole 1.α-(2,4-dichlorophenyl) phenyl acetaldehyde

To 47.1 g (0.188 mole) of 2,4-dichlorobenzophenone and 36.2 g (0.289mole) of ethyl chloroacetate is slowly added 14.9 g (0.31 mole) of 50%sodium hydride at 15°. The reaction is allowed to stir and slowly comeup to ambient temperature overnight. The reaction is added to icedwater, and made acidic with dilute hydrochloric acid. The organicmaterial is extracted out with three 200 ml portions of benzene. Theextracts are combined, washed twice with 100 ml of water and dried overanhydrous magnesium sulfate. The benzene is stripped off, and the crudeproduct is added to 35.3 g (0.53 mole) of 85% potassium hydroxide in 350ml of water. This mixture is refluxed for 20 hours, cooled and washedtwice with 200 ml of benzene. The aqueous solution is acidified and theorganic acid settles out as an oil. The oil is separated and the aqueoussolution is extracted twice with 200 ml of ether. The extracts arecombined with the oil, dried over anhydrous magnesium sulfate andconcentrated to give 30.7 g of the hydroxy acid. This residue is heatedfor 3 hours at 140° to decompose it to the crude aldehyde product (24.3g). Distillation (128°-137°/0.05 mm) gives 16.3 g (33%) of the aldehyde.

2. β-(2,4-dichlorophenyl) phenethanol

To 2.4 g (0.0615 mole) of LiAlH₄ in 140 ml of anhydrous THF is addeddropwise, at 0°, 16.3 g (0.0615 mole) of the α-(2,4-dichlorophenyl)phenyl acetaldehyde in 60 ml of anhydrous THF. When the addition iscomplete, the reaction is stirred for 2 hours at 0° and then for 16hours at ambient temperature. The reaction is then heated up to refluxfor two hours, cooled and poured into ice water. The mixture isacidified with concentrated hydrochloric acid, and the organic materialis extracted out twice with 200 ml portions of ether. The extracts arecombined, dried over anhydrous magnesium sulfate and, concentrated togive 15.5 g of crude product. Distillation (125°-39°/0.025 mm) gives10.6 g (65%) of the purified alcohol product. The material is identifiedby ir, and its purity is determined by glc.

3. β-(2,4-dichlorophenyl) phenethyl methane sulfonate

The methane sulfonate is prepared according to the method of Example 1part 3, the product is identified by ir and its purity is determined byglc.

4. 1-[β-(2,4-dichlorophenyl) phenethyl]imidazole

The imidazole is prepared by the method of Example 1 part 4, the productis recrystallized from ether acetone to give 2.6 g (32%) of thehydrochloride salt, mp 197°-8°.

EXAMPLE 70 1-[ε-(2,4-dichlorophenyl) hexyl]imidazole 1.5-(2,4-dichlorophenyl) hexan-1-ol

A slurry of m-dichlorobenzene, 735 g. (5.0 mole) and anhydrous aluminumchloride, 162 g. (1.1 mole) is cooled to 10° using an ice-water bath and1,2-epoxyhexane, 100 g. (1.0 mole) is added dropwise over a one hourperiod. The temperature of the reaction is kept below 15°. The reactionmixture is allowed to come to room temperature and stirring is continuedovernight. The reaction mixture is then poured into a 4 liter flaskcontaining ice and concentrated hydrochloric acid (50 ml.) withstirring. The aqueous and organic layers are separated and the aqueouslayer extracted three times with ether (150 ml). The combined organicextracts are washed twice with water (50 ml) and dried over magnesiumsulfate. Solvent is evaporated and vacuum distillation (160°-172°/0.1mm) gives 114 g. (46%) of product.

2. 1-[ε-(2,4-dichlorophenyl) hexyl]imidazole

The primary alcohol is converted into the sulfonate and imidazolecompound in the usual manner.

EXAMPLE 71 1-[α-Methyl-β-(2,4-dichlorophenyl)hexyl]imidazole 1.2,4-Dichlorovalerophenone

To 48.0 g. (0.398 mole) of valeryl chloride in 100.0 g. (0.680 mole) ofm-dichlorobenzene is added portionwise at less than 5°, 66.7 g. (0.5mole) of aluminum chloride. When the addition is complete, the reactionmixture is allowed to stir and slowly warm up to ambient temperature for2 hours. It is then heated at reflux for 3 hours, and stirred at roomtemperature for 16 hours. The reaction mixture is poured into icedwater, and made acidic with hydrochloric acid. The oil which formedseparates, and the aqueous phase is extracted twice with 200 ml. ofether. The oil and the extracts are combined, washed with water, driedand concentrated to give 122.2 g. of the crude product. A distillation(89°-93°/0.05 mm) gives 55.2 g. (60%) of the product.

2. α-(2,4-dichlorophenyl) hexanal

To 50.0 g (0.216 mole) of 2,4-dichlorovalerophenone in 42.4 g (0.346mole) of ethyl chloroacetate at 0° is added portionwise 8.7 g (0.363mole) of sodium hydride over a 4 hour period. When the addition iscomplete, the reaction mixture is stirred and allowed to slowly warm upto ambient temperature for 2 hours. The reaction is then poured intoiced water, and the mixture is made acidic with hydrochloric acid. Theorganic material is extracted out with ether, and the extract is driedand concentrated to give 89.2 of the crude glycidic ester. The residueis treated with 40.0 g (0.607 mole) of 85% potassium hydroxide in 400 mlof water, and the mixture is heated for 2 hours on a steambath. Thealkaline solution is washed with benzene, and acidified withhydrochloric acid. The oil which forms is extracted out with ether, andthe ether solution is dried and concentrated. The residue is dissolvedin xylene, and heated at reflux for 6 hours with carbon dioxideevolution. The solution is stripped to dryness to give 32.4 g of thecrude aldehyde. A distillation (112°-7°/0.2 mm) gave 16.6 g (31%) of theproduct.

3. 3-(2,4-dichlorophenyl) heptan-2-ol

To 14.3 g (0.088 mole) of methylmagnesium iodide in 75 ml of ether isslowly added at less than 10°, 14.5 g (0.059 mole) of theα-(2,4-dichlorophenyl) hexanal. When the addition is complete, thereaction is stirred for 1 hour then heated up to reflux for 2 hours. Thereaction is cooled and poured into water. The mixture is acidified withhydrochloric acid and the oil which separates is extracted out withether. The ether solution is dried and concentrated to give 11.7 g (76%)of the crude product.

4. 3-(2,4-dichlorophenyl) hept-2-ylmethane sulfonate

The methane sulfonate is prepared by the method of Example 1 part 3, theproduct is identified by ir and its purity determined by glc.

5. 1-[α-methyl-β-(2,4-dichlorophenyl)hexyl]imidazole

The imidazole is prepared according to the procedure of Example 1 part4, the product is identified by ir and its purity determined by glcwhich shows it contains about equal amounts of isomeric products.

EXAMPLE 72 1-[β-butyl-β-(2,4-dichlorophenyl)hexyl]imidazolehydrochloride 1. ethyl, α-butyl-α-(2,4-dichlorophenyl) hexanoate

To 4.3 g (0.09 mole) of 50% sodium hydride in 200 ml of anhydroustetrahydrofuran is added 23.6 g (0.0816 mole) of ethylα-(2,4-dichlorophenyl) hexanoate, and the reaction is heated at refluxfor 72 hours. The reaction is then stirred for 72 hours at ambienttemperature. At the end of this period 16.6 g (0.09 mole) of iodobutaneare added, and the reaction is heated at reflux for 24 hours. Thereaction is cooled and poured into iced water, and the oil which formsis separated. The aqueous phase is extracted with ether, and the extractis combined with the oil. The ether solution is dried and concentratedto give 14.2 g of crude product. A distillation (150°-70°/0.25 mm) gives13.3 g of the ester product.

2. 2-butyl-2-(2,4-dichlorophenyl) hexan-1-ol

The alcohol is formed by the method of Example 1 part 2, the pureproduct 4.8 g distills at 133°-8°/0.05 mm and is identified by nmr.

3. Imidazole Reaction

The imidazole is formed via the methane sulfonate according to themethods of Example 1 parts 3 and 4. The final product 1.5 g (28%) mp103°-5° is recrystallized from acetone-ether and is identified by nmrand elemental analysis.

EXAMPLE 73 1-[β,β-bis (p-chlorophenyl) ethyl] imidazole 1. 2,2-bis(p-chlorophenyl) ethanol

To 15.1 g (0.397 mole) of lithium aluminum hydride in 750 ml ofanhydrous tetrahydrofuran at less than 5° is added portionwise over a 2hour period 95.0 g (0.338 mole) of bis (p-chlorophenyl) acetic acid.When the addition is complete, the reaction is stirred at 5° for 4 hoursthen allowed to warm up to ambient temperature overnight. The reactionis slowly poured into iced water with resulting evolution of hydrogen.The mixture is made acidic with hydrochloric acid, and the organic phasewhich forms is separated. The aqueous phase is extracted twice with 200ml of ether and the extracts are combined with the organic phase. Theether solution is dried and concentrated to give 74.9 g of crudeproduct. This residue is distilled (157°-62°/0.05 mm) to give 35.3 g(39%) of the product.

2. Formation of Imidazole

The imidazole derivative (m.p. 80°-2°) is formed by the usual route.

EXAMPLE 74 1-[β-(o&p-chlorophenyl)p-chlorophenethyl] imidazole 1.2-(o&p-chlorophenyl)-p-chlorophenethyl chloride

To a mixture of 12.5 ml of 30% oleum in 25 ml of sulfuric acid is addeddropwise at less than 35°, 11.6 g (0.76 mole) of chloroacetaldehydediethyl acetal in 34.0 g (0.30 mole) of chlorobenzene. When the additionis complete, the reaction is stirred for 1 hour, and warmed up toambient temperature. The reaction mixture is poured into iced water, andthe organic phase is extracted out twice with 200 ml of ether. Theextracts are dried and concentrated to give 17.3 g of the yellow-orangecrude product. The material is distilled to give 9.8 g (165°-8°/0.4 mm)of the isomeric product.

2. Reaction with Imidazole

To 75 ml of methanol is added 1.05 g (0.0458 mole) of sodium to form asolution. To this solution is then added 3.1 g (0.0458 mole) ofimidazole, and the reaction is stripped to dryness. To the wet solidresidue is added 50 ml of N,N-dimethylformamide. The resulting solutionis heated up to 130°, and the remaining methanol is distilled off. Tothis dimethylformamide solution is added 8.7 g (0.0305 mole) of the2-(o&p-chlorophenyl)-p-chlorophenethyl chloride, and the reaction isheated up to 130° for 48 hours. The reaction is cooled, poured into icedwater and the organic material is extracted out with ether. The etherextract is cooled and treated with hydrogen chloride gas. The oil saltwhich formed is separated, and treated with a sodium bicarbonatesolution. The resulting mixture is extracted with ether and the ethersolution is dried and concentrated to give 0.6 g of the product.

Example 75 1-[β,β-tetramethylene-β-(2,4-dichlorophenyl)ethyl]imidazoliumnitrate 1. α,α-tetramethylene-2,4-dichlorobenzyl cyanide

Into a 500 ml three-necked flask is placed 200 ml of 25% sodiumhydroxide solution and 4 g of tetraethyl ammonium bromide. To thissuspension is added dropwise a solution of 33.5 g (0.2 mole) of2,4-dichlorobenzyl cyanide and 43 g (0.2 mole) of 1,4-dibromobutane in200 ml of methylene chloride under nitrogen. When the addition is over,the reaction mixture is heated to reflux for 1.5 hours. It is thenpoured into water and the layers are separated. The aqueous layer isextracted with 100 ml of methylene chloride. The combined organicextracts are washed with water, saturated sodium chloride solution anddried over magnesium sulfate. Solvent is evaporated to give a lightyellow oil. Vacuum distillation (130°-140°/0.2 mm) gives 30.4 g (63%) ofpure product, which is identified by nmr.

2. α,α-tetramethylene-2,4-dichlorophenyl acetic acid

A mixture of 14 g (0.06 mole) of α,α-tetramethylene-2,4-dichlorobenzylcyanide, 160 ml of 40% potassium hydroxide solution, and 120 ml ofdiethylene glycol is heated under reflux for 3 days. The reactionmixture is poured into water and extracted with ether. The aqueous layeris then made acidic with hydrochloric acid followed by extraction withether. The combined ether extracts from the acidic solution are washedwith water, saturated sodium chloride solution and then dried overmagnesium sulfate. Solvent is evaporated to give 12.4 g of crude acidwhich is recrystallized from hexane-benzene to give 8 g of pure acid,m.p. 136°-138°.

3. 2,2-tetramethylene-2-(2,4-dichlorophenyl)-ethyl alcohol

To a suspension of 3 g (0.08 mole) of lithium aluminum hydride in 300 mlof anhydrous ether is added dropwise 13 g (0.05 mole) ofα,α-tetramethylene-2,4-dichlorophenyl acetic acid in 50 ml of etherunder nitrogen. The reaction mixture is then heated to reflux for onehour. Excess lithium aluminum hydride is carefully decomposed bydropwise addition of 10% hydrochloric acid into the reaction mixture.The two layers are separated and the aqueous layer is extracted withether. The combined ether extracts are washed with water and dried overmagnesium sulfate. Solvent is evaporated to give 9.8 g of alcohol, whichis identified by nmr.

4. 2,2-tetramethylene-2-(2,4-dichlorophenyl)ethyl methane sulfonate

To a mixture of 9.8 g (0.04 mole) of2,2-tetramethylene-2-(2,4-dichlorophenyl) ethyl alcohol and 5 g (0.04mole) of methane sulfonyl chloride in 30 ml of benzene is added dropwise5 g (0.05 mole) of triethyl amine. The reaction mixture is stirred atroom temperature overnight. The precipitate formed is filtered. Thebenzene solution is washed with water then dilute hydrochloric acid anddried over magnesium sulfate. Solvent is evaporated to give 12 g ofproduct, which is identified by nmr.

5. 1-[β,β-tetramethylene-β-(2,4-dichlorophenyl) ethyl]imidazole

A mixture of 12 g (0.037 mole) of2,2-tetramethylene-2-(2,4-dichlorophenyl)ethyl methane sulfonate, 10 g(0.15 mole) of imidazole, and 1 ml of dimethyl formamide is heated at140° for 24 hours. The reaction mixture is poured into water andextracted with ether. The combined ether extracts are washed with waterand dried over magnesium sulfate. The drying agent is filtered and tothe etheral solution is added conc. nitric acid dropwise. The whiteprecipitate which forms is collected by filtration and dried undervacuo. A total of 3.7 g of the salt is obtained m.p. 176°-179°, which isidentified by nmr.

EXAMPLE 101 1-[β-(2,4-dichlorophenyl)hexyl]-4-nitroimidazole

To 1.3 g (0.0307 mole) of sodium hydroxide in 150 ml of methanol isadded 3.5 g (0.0307 mole) of 4-nitroimidazole, and the solution isheated and the methanol distilled off. To the concentrate is added 100ml of dimethyl formamide and the solution is heated up to 120° to removethe excess methanol and water. This dimethyl formamide solution is thencooled to less than 90° and 10.0 g (of 0.0307 mole) of2-(2,4-dichlorophenyl)hexyl methane sulfonate is added. The reactionmixture is heated up to 145° for two hours and then cooled and pouredinto water. The organic material is extracted out with ether and afterdrying, the extract is stripped to give 11.2 g of residue. Theconcentrate is triturated with hexane and then dissolved in 25 ml ofmethanol. The methanol solution is poured slowly into water and a gummysolid forms. This solid is separated by filtration, dried andrecrystallized from acetone-hexane to give 4.2 g (41 %) of the product,m.p. 67°-9°.

EXAMPLE 102 1-[β-(2,4-dichlorophenyl)hexyl]4,5-dichloroimidazole

To 100 ml of methanol is added 1.7 g (0.0735 moles) of sodium. When thesodium dissolves, 10 g (0.0735 moles) of 4,5-dichlorimidazole is added.The mixture is stirred until a solution forms, and then the methanol isstripped off. The wet residue is then added to 50 ml of dimethylformamide and the solution heated up to 125° to remove the remainingmethanol and water. The solution is cooled to less than 100° and 2.5 g(0.0735 moles) of 2-(2,4-dichlorophenyl)hexyl methane sulfonate isadded. The reaction is heated up to 130° for two hours and then cooled.The reaction is poured into water and the organic material extractedthree times with 200 ml of benzene. The combined extracts are washedtwice with 50 ml of water, dried over anhydrous magnesium sulfate andconcentrated to obtain 15.8 g of the crude product. The residue isdissolved in ether, and treated with dry hydrogen chloride gas. Theether solution is decanted from the oil which forms and the oil istriturated twice with 150 ml of ether. The oil is then treated with 10%sodium hydroxide, and the product extracted out twice with 200 ml ofether. The ether solution is dried and concentrated to give 12.6 g (47%)of the oil product.

EXAMPLE 103 1-[ β-(2,4-dichlorophenyl)hexyl]-3-butylimidazolium iodide

1-[β-(2,4-dichlorophenyl)hexyl]imidazole 5.0 g (0.0168 moles) is heatedfor two hours on a steambath with 3.1 g (0.0168 moles) of 1-iodobutane.The reaction is cooled and triturated three times with 50 ml of ether.The oil residue is stripped to dryness to give 5.3 g (66%) of the oilproduct.

EXAMPLE 104 1-[β-(2,4-dichloro-5-nitrophenyl)hexyl] nitroimidazole

To 1-[β-(2,4-dichlorophenyl)hexyl]imidazole 20.0 g (0.067 mole) in 40 mlof sulfuric acid is slowly added 80 ml of nitric acid and 40 ml ofsulfuric acid. The reaction is heated on a steambath for 14 hours,cooled and poured into water. The aqueous acidic solution is decantedfrom the oil which forms. The residue is washed twice with 75 ml ofwater, and then taken up in acetone-benzene, dried and concentrated togive 14.9 g of the crude product. To purify, 3.0 g of the crude productis dissolved in hot methanol. Upon cooling the product precipitates outis separated by filtration and dried to give 1.6 g of the nitroimidazole derivative.

The following Tables I and II present some of the compounds prepared byprocedures presented in the preceding examples. These tables arepresented as a further illustration of the types of compoundsencompossed by the present invention and are not to be construed inanyway as limitations of the scope of this invention.

                                      TABLE I                                     __________________________________________________________________________     ##STR21##                                                                    Example No.                                                                           Z             (A).sub.n                                                                          R.sup.1    R.sup.2                                                                            (B).sub.n'                                                                          (X).sub.a                                                                           MY                     __________________________________________________________________________    1       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     2       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                    3       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    1/2 ZnCl.sub.2         4       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    C.sub.2 H.sub.2                                                               O.sub.4                5       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    1/2 CuBr.sub.2         6       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    1/2 CuSO.sub.4         7       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    1/2 CoCl.sub.2         8       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    1/2 NiSO.sub.4         9       2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    1/2 FeCl.sub.2         __________________________________________________________________________     ##STR22##                                                                    Example No.                                                                           Z             (A).sub.n                                                                          R.sup.1    R.sup.2                                                                            (B).sub.n'                                                                          (X).sub.a                                                                           MY                     __________________________________________________________________________    10      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    1/2 Cr(NO.sub.3).su                                                           b.3                    11      2,6-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                    12      2-CH.sub.3 C.sub.6 H.sub.4                                                                  --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     13      3-CH.sub. 3 C.sub.6 H.sub.4                                                                 --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     14      4-CH.sub.3 C.sub.6 H.sub.4                                                                  --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                    15      4-CH.sub.3 OC.sub.6 H.sub.4                                                                 --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     16      C.sub.6 H.sub.5                                                                             --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     17      4-ClC.sub.6 H.sub.4                                                                         --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                    18      4-ClC.sub.6 H.sub.4                                                                         --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     19      3-ClC.sub.6 H.sub.4                                                                         --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     20      2-ClC.sub.6 H.sub.4                                                                         --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                     ##STR23##                                                                    Example No.                                                                           Z             (A).sub.n                                                                          R.sup.1    R.sup.2                                                                            (B).sub.n'                                                                          (X).sub.a                                                                           MY                     __________________________________________________________________________    21      3,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     22      2,4-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                        --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     23      3-CF.sub. 3 C.sub.6 H.sub.4                                                                 --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     24      4-FC.sub.6 H.sub.4                                                                          --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     25      4-BrC.sub.6 H.sub.4                                                                         --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                    26      4-CH.sub.3 SC.sub.6 H.sub.4                                                                 --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HNO.sub.3              27      4-CH.sub.3 SO.sub.2 C.sub.6 H.sub.4                                                         --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     28      4(t-C.sub.4 H.sub.9)C.sub.6 H.sub.4                                                         --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     29      4-NO.sub.2 C.sub.6 H.sub.4                                                                  --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     30      4-NH.sub.2 C.sub.6 H.sub.4                                                                  --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     31      2,4-Cl.sub.2 -5-NO.sub.2 C.sub.6 H.sub.2                                                    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                    32      2,6-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                        --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                    33      3,5-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                        --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     34      C.sub.6 H.sub.5 -C.sub.6 H.sub.5                                                            --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     35                                                                                     ##STR24##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.                                                                             --    --                     36                                                                                     ##STR25##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    2 . HNO.sub.3          37                                                                                     ##STR26##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    C.sub.2 H.sub.2                                                               O.sub.4                38                                                                                     ##STR27##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     39                                                                                     ##STR28##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     40                                                                                     ##STR29##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     41                                                                                     ##STR30##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     42                                                                                     ##STR31##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     43                                                                                     ##STR32##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     44                                                                                     ##STR33##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     45                                                                                     ##STR34##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     46                                                                                     ##STR35##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     47                                                                                     ##STR36##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     48                                                                                     ##STR37##    --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     49      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   CH.sub.2 CHCH.sub.2                                                                      H    CH.sub.2                                                                            --    HNO.sub.3              50      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   4-ClC.sub.6 H.sub.4 CH.sub.2                                                             H    CH.sub.2                                                                            --    --                     51      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   (CH.sub.2).sub.2 C.sub.6 H.sub.4 F-4                                                     H    CH.sub. 2                                                                           --    HCl                    52      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.6 H.sub.11                                                                         H    CH.sub.2                                                                            --    2H.sub.2 O . HCl       53                                                                                     ##STR38##    --   CH.sub.3   H    CH.sub.2                                                                            --    --                     54                                                                                     ##STR39##    --   CH.sub.3   H    CH.sub.2                                                                            --    --                     55                                                                                     ##STR40##    --   C.sub.2 H.sub.5                                                                          H    CH.sub.2                                                                            --    HNO.sub.3              56                                                                                     ##STR41##    --   C.sub.2 H.sub.5                                                                          H    CH.sub.2                                                                            --    --                     57                                                                                     ##STR42##    --   C.sub.2 H.sub.5                                                                          H    CH.sub.2                                                                            --    --                     58                                                                                     ##STR43##    --   C.sub.2 H.sub.5                                                                          H    CH.sub.2                                                                            --    --                     59                                                                                     ##STR44##    --   C.sub.6 H.sub.13 n                                                                       H    CH.sub.2                                                                            --    --                     60                                                                                     ##STR45##    --   C.sub.6 H.sub.13 n                                                                       H    CH.sub.2                                                                            --    --                     61                                                                                     ##STR46##    --   C.sub.6 H.sub.13 n                                                                       H    CH.sub.2                                                                            --    --                     62                                                                                     ##STR47##    CH.sub.2                                                                           C.sub.4 H.sub.9 n                                                                        H    --    --    --                     63      2,4,6(CH.sub.3).sub.3 C.sub.6 H.sub.2                                                       CH.sub.2                                                                           C.sub.6 H.sub.13 n                                                                       H    --    --    --                     64      2,4,6-(CH.sub.3).sub.3 C.sub.6 H.sub.2                                                      CH.sub.2                                                                           C.sub.2 H.sub.5                                                                          H    --    --    --                     65      2,4,6-(CH.sub.3).sub.3 C.sub.6 H.sub.2                                                      CH.sub.2                                                                           C.sub.4 H.sub.9 n                                                                        H    --    --    --                     66      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                CH.sub.2                                                                           C.sub.4 H.sub.9 n                                                                        H    --    --    --                     67      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                CH.sub.2                                                                           C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     68      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    (CH.sub.2).sub.2                                                                    --    --                     69      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.6 H.sub.5                                                                          H    CH.sub.2                                                                            --    HCl                    70      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   CH.sub.3   H    (CH.sub.2).sub.4                                                                    --    --                     71      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CHCH.sub.3                                                                          --    --                     72      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        C.sub.4 H.sub.9 n                                                                  CH.sub.2                                                                            --    HCl                    73      4-ClC.sub.6 H.sub.4                                                                         --   4-ClC.sub.6 H.sub.4                                                                      H    CH.sub.2                                                                            --    --                     74      4-ClC.sub.6 H.sub.4                                                                         --                                                                                  ##STR48## H    CH.sub.2                                                                            --    --                      75      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --                                                                                 ##STR49##       CH.sub.2                                                                            --    HNO.sub.3             76      4-CH.sub.3 C.sub.6 H.sub.4                                                                  --   4-CH.sub.3 C.sub.6 H.sub.4                                                               H    CH.sub.2                                                                            --    HCl                    77      4-BrC.sub.6 H.sub.4                                                                         --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    --                     78      4-ClC.sub.6 H.sub.4                                                                         --   4-ClC.sub.6 H.sub.4                                                                      H    CH.sub.2                                                                            --    HCl                    79      4-ClC.sub.6 H.sub.4                                                                         --   2-ClC.sub.6 H.sub.4                                                                      H    CH.sub.2                                                                            --    --                     80      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                (CH.sub.2).sub.2                                                                   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            --    HCl                    81      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   H          H    CH.sub.2                                                                            --    HNO.sub.3              82      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   CH.sub.3   H    CH.sub.2                                                                            --    HCl                    83      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   CH.sub.3   H    CH.sub.2                                                                            --    --                     84      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.2 H.sub.5                                                                          H    CH.sub.2                                                                            --    --                     85      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.6 H.sub.13 n                                                                       H    CH.sub.2                                                                            --    --                     86      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.8 H.sub.17 n                                                                       H    CH.sub.2                                                                            --    --                     87      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.10 H.sub.21 n                                                                      H    CH.sub.2                                                                            --    --                     88      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   CH.sub.2 CH(CH.sub.3).sub.2                                                              H    CH.sub.2                                                                            --    --                     89      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.6 H.sub.5 CH.sub.2                                                                 H    CH.sub.2                                                                            --    --                     90      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub. 6 H.sub.5 (CH.sub.2).sub.2                                                        H    CH.sub.2                                                                            --    --                     91      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.6 H.sub.9                                                                          H    CH.sub.2                                                                            --    HCl                    92      C.sub.6 H.sub.5                                                                             --   C.sub.6 H.sub.5                                                                          H    CH.sub.2                                                                            --    HCl                    93      4-Cl-C.sub.6 H.sub.4                                                                        --   C.sub.6 H.sub.5                                                                          H    CH.sub.2                                                                            --    --                     94      2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                CH.sub.2                                                                           CH.sub.3   H    --    --    --                     95      C.sub.6 H.sub.5                                                                             CH.sub.2                                                                           C.sub.4 H.sub.9 n                                                                        H    --    --    --                     96      C.sub.6 H.sub.5                                                                             CH.sub.2                                                                           CH.sub.3   H    --    --    --                     97      C.sub.6 H.sub.5                                                                             --   CH.sub.3   CH.sub.3                                                                           CH.sub.2                                                                            --    HCl                    98      2 or 4-ClC.sub.6 H.sub.4                                                                    --   CH.sub.3   H    (CH.sub.2).sub.2                                                                    --    --                     99      4Cl-C.sub.6 H.sub.4                                                                         --   CH.sub.3   CH.sub.3                                                                           CH.sub.2                                                                            --    HCl                    100     2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            2-CH.sub.3                                                                          --                     101     2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            4-NO.sub.2                                                                          H.sub.2 O              102     2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            4,5-Cl.sub.2                                                                        --                     103     2,4-Cl.sub.2 C.sub.6 H.sub.3                                                                --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            3-C.sub.4 H.sub.9                                                                   HI                     104     2,4-Cl.sub.25-NO.sub.2 C.sub.6 H.sub.2                                                      --   C.sub.4 H.sub.9 n                                                                        H    CH.sub.2                                                                            NO.sub.2                                                                            --                     __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    Example                                                                            Elemental Analyses (Calc'd)                                              Number                                                                             mp.  C   H   Cl  N   O     Other                                         __________________________________________________________________________              60.64                                                                             6.16                                                                              24.01                                                                             9.16                                                     1   conc.                                                                              (60.62)                                                                           (6.10)                                                                            (23.86)                                                                           (9.42)                                                            51.48                                                                             5.60                                                                              30.30                                                                             7.89                                                     2   139-41                                                                             (53.99)                                                                           (5.74)                                                                            (31.87)                                                                           (8.40)                                                            48.75                                                                             4.94                                                                              29.70                                                                             6.88      7.58                                           3   57-63                                                                              (49.31)                                                                           (4.97)                                                                            (29.11)                                                                           (7.67)    Zn = (8.95)                                             54.22                                                                             5.33                                                                              19.20                                                                             7.56                                                                              14.16                                                4   126-8                                                                              (52.73)                                                                           (5.21)                                                                            (18.31)                                                                           (7.23)                                                                            (16.53)                                                       38.00                                                                             3.92                                                                              16.26                                                                             5.87      13.00                                          5   219-21                                                                             (44.06)                                                                           (4.44)                                                                            (17.34)                                                                           (6.85)    Cu = (7.77)                                             52.35                                                                             5.38                                                                              21.08                                                                             7.51                                                                              5.49  4.70                                           6   61-4 (47.79)                                                                           (4.81)                                                                            (18.81)                                                                           (7.43)                                                                            (8.49)                                                                              Cu = (8.43)                                             49.68                                                                             5.16                                                                              7.10                                                                              28.45     7.60                                           7   53-8 (49.75)                                                                           (5.01)                                                                            (7.73)                                                                            (29.37)   Co = (8.14)                                             45.75                                                                             4.87                                                                              18.96                                                                             6.91                                                                              10.54 5.23                                           8   107-113                                                                            (48.05)                                                                           (4.84)                                                                            (15.23)                                                                           (7.47)                                                                            (8.53)                                                                              Ni = (4.23)                                             49.77                                                                             5.13                                                                              30.12                                                                             6.92      5.70                                           9   45.50                                                                              (49.96)                                                                           (5.03)                                                                            (29.49)                                                                           (7.77)    Fe = (7.74)                                             40.67                                                                             4.81                                                                              16.78                                                                             10.14                                                                             18.97 3.2                                           10   44-9 (43.28)                                                                           (4.36)                                                                            (17.03)                                                                           (11.78)                                                                           (17.29)                                                                             Cr = (6.24)                                             53.63                                                                             5.74                                                                              31.79                                                                             8.26                                                    11   154-6                                                                              (53.99)                                                                           (5.74)                                                                            (31.87)                                                                           (8.39)                                                            77.93                                                                             9.21    11.32                                                   12   conc.                                                                              (79.29)                                                                           (9.15)                                                                            --  (11.56)                                                           78.36                                                                             9.11    11.75                                                   13   conc.                                                                              (79.29)                                                                           (9.15)                                                                            --  (11.56)                                                           68.65                                                                             8.47                                                                              12.21                                                                             9.75                                                    14   126-8                                                                              (68.92)                                                                           (8.32)                                                                            (12.71)                                                                           (10.05)                                                           72.99                                                                             8.42    11.20                                                                             7.35                                                15   conc.                                                                              (74.40)                                                                           (8.58)                                                                            --  (10.84)                                                                           (6.17)                                                        77.36                                                                             8.70    11.87                                                   16   conc.                                                                              (78.90)                                                                           (8.83)                                                                            --  (12.27)                                                           56.82                                                                             6.26                                                                              22.24                                                                             8.91                                                    17   72-3 (60.21)                                                                           (6.74)                                                                            (23.70)                                                                           (9.36)                                                            66.80                                                                             7.25                                                                              14.72                                                                             9.52                                                    18   conc.                                                                              (68.56)                                                                           (7.29)                                                                            (13.49)                                                                           (10.66)                                                           66.08                                                                             7.19                                                                              12.78                                                                             10.25                                                   19   conc.                                                                              (68.56)                                                                           (7.29)                                                                            (13.49)                                                                           (10.66)                                                           56.76                                                                             6.32                                                                              22.09                                                                             8.23                                                    20   103-6                                                                              (60.21)                                                                           (6.74)                                                                            (23.70)                                                                           (9.36)                                                            60.25                                                                             6.27                                                                              24.91                                                                             8.30                                                    21   conc.                                                                              (60.61)                                                                           (6.10)                                                                            (23.85)                                                                           (9.42)                                                            78.06                                                                             9.46    10.83                                                   22   conc.                                                                              (79.64)                                                                           (9.44)                                                                            --  (10.93)                                                           63.31                                                                             6.34    10.84     18.62                                         23   conc.                                                                              (64.85)                                                                           (6.46)                                                                            --  (9.45)    F = (19.23)                                             72.06                                                                             8.05    10.20     7.96                                          24   conc.                                                                              (73.14)                                                                           (7.77)                                                                            --  (11.37)   F = (7.71)                                              51.62                                                                             6.00                                                                              9.15                                                                              7.62      22.76                                         25   conc.                                                                              (52.42)                                                                           (5.87)                                                                            10.32                                                                             (8.15)    Br = (23.25)                                            56.48                                                                             6.81    13.06                                                                             13.89 9.32                                          26   108-10                                                                             (56.95)                                                                           (6.87)                                                                            --  (12.45)                                                                           (14.22)                                                                             S = 9.50                                                62.06                                                                             7.48    8.57                                                                              10.86 9.62                                          27   conc.                                                                              (62.71)                                                                           (7.24)                                                                            --  (9.14)                                                                            (10.44)                                                                             S = (10.47)                                             79.96                                                                             10.06   9.75                                                    28   conc.                                                                              (80.23)                                                                           (9.92)                                                                            --  (9.85)                                                            65.40                                                                             7.19    15.42                                                                             12.58                                               29   conc.                                                                              (65.91)                                                                           (7.01)                                                                            --  (15.37)                                                                           11.71                                                         73.64                                                                             8.92    16.84                                                   30   conc.                                                                              (74.03)                                                                           (8.70)  (17.27)                                                           45.37                                                                             5.11                                                                              26.73                                                                             10.55                                                                             11.72                                               31   99-100                                                                             (45.41)                                                                           (5.06)                                                                            (26.81)                                                                           (10.59)                                                                           (12.09)                                                       78.23                                                                             9.85    10.77                                                   32   conc.                                                                              (79.64)                                                                           (9.44)                                                                            --  (10.93)                                                           78.97                                                                             9.79    10.54                                                   33   conc.                                                                              (79.64)                                                                           (9.44)                                                                            --  (10.93)                                                           79.73                                                                             7.71    8.75                                                    34   conc.                                                                              (82.85)                                                                           (7.95)                                                                            --  (9.20)                                                            66.46                                                                             7.79    11.70     13.42                                         35   conc.                                                                              (66.62)                                                                           (7.74)                                                                            --  (11.95)   S = (13.68)                                             47.38                                                                             6.06    19.96                                                                             26.24                                               36   103-5                                                                              (47.32)                                                                           (5.96)                                                                            --  (19.71)                                                                           (27.01)                                                       61.90                                                                             6.49    11.88                                                                             20.59                                               37   128-30                                                                             (62.27)                                                                           (6.60)                                                                            --  (11.46)                                                                           (21.83)                                                       81.47                                                                             8.17    9.41                                                    38   conc.                                                                              (82.00)                                                                           (7.95)                                                                            --  (10.05)                                                           78.95                                                                             7.80    9.25                                                    39   conc.                                                                              (82.00)                                                                           (7.95)                                                                            --  (10.05)                                                           78.20                                                                             9.99    9.34                                                    40   conc.                                                                              (80.23)                                                                           (9.92)                                                                            --  (9.85)                                                            74.50                                                                             9.51    9.67                                                    41   conc.                                                                              (79.94)                                                                           (9.69)                                                                            --  (10.36)                                                           79.63                                                                             9.48    9.87                                                    42   conc.                                                                              (80.55)                                                                           (9.01)                                                                            --  (10.44)                                                           76.36                                                                             9.50    10.32                                                   43   conc.                                                                              (79.64)                                                                           (9.44)                                                                            --  (10.93)                                                           76.82                                                                             9.46    10.13                                                   44   conc.                                                                              (79.64)                                                                           (9.44)                                                                            --  (10.93)                                                           77.50                                                                             9.30    10.46                                                   45   conc.                                                                              (78.28)                                                                           (9.15)                                                                            --  (11.56)                                                           78.81                                                                             9.73    10.36                                                   46   conc.                                                                              (79.64)                                                                           (9.44)                                                                            --  (10.93)                                                           78.30                                                                             8.49    9.19                                                    47   conc.                                                                              (82.00)                                                                           (7.95)                                                                            --  (10.05)                                                           81.12                                                                             8.21    9.68                                                    48   conc.                                                                              (82.85)                                                                           (7.95)                                                                            --  (9.20)                                                            48.87                                                                             4.44                                                                              20.94                                                                             11.92                                                                             13.44                                               49   108-10                                                                             (48.85)                                                                           (4.39)                                                                            (20.60)                                                                           (12.21)                                                                           (13.95)                                                       58.68                                                                             4.54                                                                              28.86                                                                             7.44                                                    50   conc.                                                                              (59.12)                                                                           (4.13)                                                                            (29.09)                                                                           (7.66)                                                            57.04                                                                             4.58                                                                              26.60                                                                             7.17      4.50                                          51   152-3                                                                              (57.08)                                                                           (4.54)                                                                            (26.61)                                                                           (7.01)    F = (4.75)                                              52.05                                                                             5.62                                                                              26.82                                                                             7.78                                                    52   conc.                                                                              (51.55)                                                                           (5.85)                                                                            (26.85)                                                                           (7.07)                                                            74.45                                                                             8.90    11.92                                                   53   conc.                                                                              (78.46)                                                                           (8.46)                                                                            --  (13.09)                                                           76.82                                                                             8.23    13.75                                                   54   conc.                                                                              (77.96)                                                                           (8.05)                                                                            --  (13.99)                                                           62.28                                                                             7.16    13.87                                                   55   111-2                                                                              (63.35)                                                                           (6.98)                                                                            --  (13.85)                                                           78.48                                                                             9.18    11.56                                                   56   conc.                                                                              (78.90)                                                                           (8.83)                                                                            --  (12.27)                                                           77.14                                                                             8.54    12.96                                                   57   conc.                                                                              (78.46)                                                                           (8.46)                                                                            --  (13.09)                                                           77.71                                                                             8.94    11.74                                                   58   conc.                                                                              (78.90)                                                                           (8.83)                                                                            --  (12.27)                                                           79.35                                                                             10.03   9.14                                                    59   conc.                                                                              (80.23)                                                                           (9.92)                                                                            --  (9.85)                                                            79.47                                                                             9.70    9.27                                                    60   conc.                                                                              (79.94)                                                                           (9.69)                                                                            --  (10.36)                                                           78.29                                                                             9.88    8.85                                                    61   conc.                                                                              (80.23)                                                                           (9.92)                                                                            --  (9.85)                                                            70.60                                                                             8.10    9.90                                                    62   conc.                                                                              (70.80)                                                                           (8.39)                                                                            --  (9.72)                                                            78.80                                                                             10.21   8.93                                                    63   conc.                                                                              (80.48)                                                                           (10.13)                                                                           --  (9.39)                                                            76.70                                                                             9.29    10.94                                                   64   conc.                                                                              (79.28)                                                                           (9.15)                                                                            --  (11.56)                                                           79.75                                                                             9.96    10.20                                                   65   conc.                                                                              (79.94)                                                                           (9.69)                                                                            --  (10.36)                                                           59.93                                                                             6.14                                                                              22.52                                                                             9.10                                                    66   conc.                                                                              (60.61)                                                                           (6.10)                                                                            (23.86)                                                                           (9.43)                                                            61.31                                                                             6.86                                                                              23.28                                                                             8.62                                                    67   conc.                                                                              (61.74)                                                                           (6.48)                                                                            (22.78)                                                                           (9.00)                                                            60.46                                                                             6.21                                                                              23.99                                                                             8.13                                                    68   conc.                                                                              (61.74)                                                                           (6.48)                                                                            (22.78)                                                                           (9.00)                                                            58.82                                                                             4.38                                                                              28.44                                                                             8.04                                                    69   197-8                                                                              (57.73)                                                                           (4.28)                                                                            (30.07)                                                                           (7.92)                                                            60.39                                                                             6.46                                                                              23.50                                                                             8.94                                                    70   conc.                                                                              (60.62)                                                                           (6.10)                                                                            (23.86)                                                                           (9.42)                                                            61.33                                                                             6.42                                                                              23.10                                                                             8.34                                                    71   conc.                                                                              (61.74)                                                                           (6.48)                                                                            (22.78)                                                                           (9.00)                                                            54.93                                                                             6.54                                                                              25.44                                                                             6.70                                                    72   103-5                                                                              (58.55)                                                                           (6.98)                                                                            (27.29)                                                                           (7.19)                                                            64.59                                                                             4.44                                                                              21.81                                                                             8.65                                                    73   80-2 (64.37)                                                                           (4.45)                                                                            (22.35)                                                                           (8.83)                                                  74   conc.                                                                              49.78                                                                             4.78                                                                              20.07                                                                             11.60                                                                             13.86                                               75   176-9                                                                              (50.29)                                                                           (4.78)                                                                            (19.79)                                                                           (11.79)                                                                           (13.40)                                                       69.42                                                                             6.81                                                                              11.15                                                                             8.75                                                    76   195-7                                                                              (72.92)                                                                           (6.77)                                                                            (11.33)                                                                           (8.96)                                                            57.40                                                                             6.01                                                                              --  8.25                                                                              Br = 28.58                                          77   conc.                                                                              (58.64)                                                                           (6.23)  (9.12)                                                                            (26.01)                                                       58.00                                                                             4.11                                                                              29.89                                                                             7.69                                                    78   248-50                                                                             (57.73)                                                                           (4.28)                                                                            (30.07)                                                                           (7.92)                                                            63.38                                                                             4.60                                                                              22.11                                                                             8.03                                                    79   conc.                                                                              (64.30)                                                                           (4.41)                                                                            (22.40)                                                                           (8.85)                                                            56.50                                                                             6.54                                                                              28.83                                                                             7.97                                                    80   137-8                                                                              (56.44)                                                                           (6.41)                                                                            (29.40)                                                                           (7.75)                                                            43.13                                                                             3.74                                                                              22.98                                                                             13.99                                                   81   109-11                                                                             (43.42)                                                                           (3.61)                                                                            (23.35)                                                                           (13.81)                                                           49.20                                                                             4.54                                                                              36.07                                                                             9.60                                                    82   163-6                                                                              (49.42)                                                                           (4.49)                                                                            (36.47)                                                                           (9.61)                                                            56.68                                                                             4.88                                                                              27.37                                                                             11.11                                                   83   conc.                                                                              (56.49)                                                                           (4.74)                                                                            (27.79)                                                                           (10.98)                                                           56.95                                                                             5.33                                                                              26.26                                                                             10.02                                                   84   conc.                                                                              (58.01)                                                                           (5.24)                                                                            (26.34)                                                                           (10.41)                                                           61.92                                                                             6.84                                                                              22.27                                                                             8.57                                                    85   conc.                                                                              (62.77)                                                                           (6.82)                                                                            (21.80)                                                                           (8.61)                                                            63.16                                                                             7.23                                                                              19.54                                                                             7.17                                                    86   conc.                                                                              (64.59)                                                                           (7.42)                                                                            (20.07)                                                                           (7.93)                                                            65.32                                                                             8.05                                                                              18.35                                                                             5.84                                                    87   conc.                                                                              (66.00)                                                                           (7.86)                                                                            (18.65)                                                                           (7.35)                                                            57.92                                                                             6.36                                                                              23.16                                                                             9.25                                                    88   conc.                                                                              (60.60)                                                                           (6.07)                                                                            (23.90)                                                                           (9.43)                                                            64.42                                                                             5.01                                                                              21.85                                                                             8.13                                                    89   conc.                                                                              (65.27)                                                                           (4.87)                                                                            (21.41)                                                                           (8.46)                                                            64.31                                                                             5.31                                                                              20.75                                                                             7.71                                                    90   conc.                                                                              (66.19)                                                                           (5.25)                                                                            (20.54)                                                                           (8.11)                                                            54.33                                                                             5.39                                                                              28.91                                                                             7.38                                                    91   175-7                                                                              (57.08)                                                                           (5.35)                                                                            (29.73)                                                                           (7.83)                                                            62.62                                                                             6.38                                                                              11.98                                                                             8.88                                                    92   83-5 (71.70)                                                                           (6.02)                                                                            (12.45)                                                                           (8.94)                                                            71.38                                                                             5.41                                                                              12.81                                                                             9.90                                                    93   conc.                                                                              (72.21)                                                                           (5.35)                                                                            (12.54)                                                                           (9.91)                                                            55.59                                                                             4.96                                                                              27.14                                                                             11.30                                                   94   conc.                                                                              (56.49)                                                                           (4.74)                                                                            (27.79)                                                                           (10.98)                                                           76.62                                                                             8.67    12.52                                                   95   conc.                                                                              (78.90)                                                                           (8.83)                                                                            --  (12.27)                                                           76.58                                                                             7.57    15.08                                                   96   conc.                                                                              (77.38)                                                                           (7.58)                                                                            --  (15.04)                                                           58.92                                                                             6.64                                                                              15.61                                                                             12.56                                                   97   165 dec.                                                                           (65.95)                                                                           (7.24)                                                                            (14.98)                                                                           (11.83)                                                           65.70                                                                             6.74                                                                              15.09                                                                             11.58                                                   98   conc.                                                                              (66.52)                                                                           (6.44)                                                                            (15.10)                                                                           (11.93)                                                           53.56                                                                             6.15                                                                              25.16                                                                             11.13                                                   99   168-75                                                                             (57.58)                                                                           (5.95)                                                                            (26.15)                                                                           (10.33)                                                           58.73                                                                             6.70                                                                              23.79                                                                             7.86                                                    100  conc.                                                                              (61.74)                                                                           (6.47)                                                                            (22.78)                                                                           (9.00)                                                            50.65                                                                             4.90                                                                              19.39                                                                             11.63                                                                             13.54                                               101  67-9 (50.05)                                                                           (5.23)                                                                            (19.70)                                                                           (11.67)                                                                           (13.33)                                                       50.55                                                                             4.83                                                                              38.62                                                                             6.59                                                    102  conc.                                                                              (49.21)                                                                           (4.40)                                                                            (38.74)                                                                           (7.65)                                                            47.67                                                                             5.98                                                                              15.39                                                                             5.87      24.39                                         103  conc.                                                                              (47.42)                                                                           (5.66)                                                                            (14.73)                                                                           (5.82)    I = (26.37)                                             46.60                                                                             4.20                                                                              18.34                                                                             14.37                                                                             17.00                                               104  conc.                                                                              (46.53)                                                                           (4.17)                                                                            (18.31)                                                                           (14.47)                                                                           (16.53)                                             __________________________________________________________________________

The metal salt complexes of the above 1-substituted aralkyl imidazolescan be prepared by adding dropwise, with stirring, a stoichiometricamount of a metal salt dissolved in an appropriate solvent to a solutionof the 1-substituted aralkyl imidazole dissolved in a similarlyappropriate solvent. The reaction mixture is briefly stirred and thesolvent is removed under reduced pressure to give the metal salt complexof the respective 1-substituted aralkyl imidazole. Identification andpurity are determined by elemental analysis.

The metal salt complexes can also be prepared by mixing stoichiometricor excess amounts of the metal salt and 1-substituted aralkyl imidazolein the desired amount of solvent containing the appropriate adjuvantsjust prior to spraying the plants. Adjuvants that may be included inthis "in-situ" preparation may be detergents, emulsifiers, wettingagents, spreading agents, dispersing agents, stickers, adhesives, andthe like which are used in agricultural applications.

Solvents that can be utilized in these procedures include any polarsolvent, e.g., water, methanol, ethanol, isopropanol or ethylene glycoland any aprotic dipolar solvent e.g., dimethylsulfoxide, acetonitrile,dimethylformamide, nitromethane or acetone.

The metal salt cations that may be used in these procedures can beselected from the group consisting of calcium, magnesium, manganese,copper, nickel, zinc, iron, cobalt, tin, cadmium, mercury, chromium,lead and barium and the like.

Any appropriate anion e.g., chloride, bromide, iodide, sulfate,bisulfate, phosphate, nitrate, perchlorate, carbonate, bicarbonate,hydrosulfide, hydroxide, acetate, oxalate, malate, citrate and the likemay be utilized as the counterion in the metal salt.

It has also been found that any metal containing fungicides can also actas safening agents when used in place of metal salts. Typical metalcontaining fungicides that can be utilized in these procedures are: (a)dithiocarbamates and derivatives such as: ferric dimethyldithiocarbamate(ferbam), zinc dimethyldithiocarbamate (ziram), manganeseethylenebisdithiocarbamate (maneb) and its coordination product withzinc ion (mancozeb), zinc ethylenebisdithiocarbamate (zineb); (b)copper-based fungicides such as: cuprous oxide, copper naphthenate, andBordeaux mixture; and (c) miscellaneous fungicides such as:phenylmercuric acetateN-ethylmercuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide,phenylmercuri monoethanolammonium lactate, nickel-containing compoundsand calcium cyanamide.

The compounds and metal salt complexes of this invention are excellentas systemic protectant/eradicant fungicides and possess a high degree ofactivity against assorted phytopathogenic fungi. Certain compounds areparticularly effective for the control of grey mold of faba beans(Botyrytis cinerea), rice blast (Piricularia oryzae) on rice plants,tomato late blight (Phytophtora infestans) on tomato seedlings, beanpowdery mildew (Erysiphe polygoni) on bean plants, barley net blotch(Helminthosporium teres) on barley plants, grape downy mildew(Plasmopora viticola) on grape seedlings, citrus decay (Penicilliumdigitatum) on citrus fruit, apple scab (Venturia inaequalis) on appleseedlings, wheat powdery mildew (Erysiphe graminis) on wheat plants,wheat black point (Alternaria tenius on wheat plants, black rot ofgrapes (Guignardia bidwellii) on grape seedlings, cucumber powderymildew (Erysiphe cichoracearum) on cucumber plants, and the organismresponsible for the production of aflatoxin (Aspergillus flavus).

The compounds eradicant fungicidal properties are unique in that theykill Helminthosporium teres in infected plant tissues a property notpossessed by current fungicides used to control diseases incited byHelminthosporium spp. The systemic properties possessed by thesecompounds are equally unique in their ability to move both acropetallyand basipetally in plant tissues.

As the free base these compounds can be used to control seedborneHelminthosporium oryzae a property which is found in no other fungicidesother than the organic mercury compounds.

These compounds as the free base possess growth regulatory activity inboth dicotyledonous and monocotyledonous plants, the most pronouncedeffect being a retardation of plant growth. In some cases, particularlyin dicotyledonous plants, some of the growth regulatory properties maybe considered adverse. When this occurs, the growth regulatory andphytotoxic plant responses may be suppressed by metal salt complexationof the imidazole compounds with elements selected from Groups IIA, IVA,VA, IB, IIB, VIB, VIIB and VIII of the Periodic Table.

In evaluating these compounds, a preliminary fungicidal evaluation iscarried out using the compounds at 300 ppm and spraying the plants torun off in a carrier volume of about 150 gallons/acre.

The general procedure is to take potted plants in proper condition ofgrowth for susceptibility to the fungal disease to be evaluated to spraythese on a moving belt and allow to dry. The proper plants are theninoculated with the fungal spores and then allowed to incubate until thedisease has developed and the control read or estimated. The percentdisease control is reported by the following rating system:

A=97-100% control

B=90-96% control

C=70-89% control

D=50-69% control

E=Inactive<50% control

    % disease control=disease of untreated-disease of treated×100 disease of untreated

The phytopathogenic fungi used in the evaluation of the fungicidalactivity of the compounds and salts of this invention are describedbelow.

BH--barley net blotch (Helminthosporium teres)

BOT--grey mold of faba beans (Botyrytis cinerea)

BPM--bean powdery mildew (Erysiphe polygoni)

GDM--grape downy mildew (Plasmopora viticola)

TLB--tomato late blight (Phytophtora infestans)

RB--rice blast (Piricularia oryzae)

WSR--wheat stem rust (Puccinia graminis f. sp. tritici)

WLR--wheat leaf rust (Puccinia recondita)

Table III presents the results of the application of some of thecompounds and salts of this invention at a rate of 300 ppm evaluatedagainst the above fungi.

                  TABLE III                                                       ______________________________________                                        Ex-                                                                           ample                                                                         No.   BH     BOT    BPM  GDM   TLB  RB   WSR   WLR                            ______________________________________                                        1     A      B      A    B     E    B    --    A                              2     A      B      A    A     B    A    --    A                              3     A      A      A    A     B    B    --    A                              4     E      B      A    A     A    B    --    A                              5     A      C      A    A     B    E    --    A                              6     A      A      A    B     B    E    --    A                              7     A      A      A    A     A    A    --    A                              8     A      A      A    A     B    B    --    A                              9     A      A      A    A     A    A    --    A                              10    A      A      A    A     B    A    --    A                              11    E      E      A    B     B    B    --    A                              12    A      E      A    E     B    A    --    A                              13    E      E      A    --    E    E    --    E                              14    A      E      A    B     A    --   --    E                              15    A      E      A    B     E    B    --    C                              16    A      E      E    E     C    A    --    C                              17    A      E      A    B     A    E    --    B                              18    A      E      A    A     A    E    --    A                              19    E      E      A    B     B    B    --    A                              20    A      E      A    B     A    E    --    A                              21    A      B      A    B     B    B    --    A                              22    A      E      A    A     A    B    --    A                              23    E      E      E    E     E    --   E     --                             24    A      C      A    C     E    --   C     --                             25    A      C      A    E     E    --   E     --                             26    E      C      A    E     E    --   E     --                             27    --     E      E    E     --   --   E     --                             28    --     E      A    E     B    --   B     --                             29    A      C      A    C     E    --   C     --                             30    E      E      B    C     E    A    A     --                             31    E      C      A    E     E    --   E     --                             32    B      A      A    E     E    --   C     --                             33    E      C      A    C     B    --   E     --                             34    E      C      A    C     E    --   B     --                             35    A      E      A    C     E    --   E     --                             36    E      E      A    E     E    --   E     --                             37                                                                            38    A      E      A    B     A    --   B     --                             39                                                                            40    A      E      A    E     E    --   E     --                             41    E      C      A    E     --   --   E     --                             42    E      E      A    C     A    --   C     --                             43    E      C      A    C     E    --   E     --                             44    E      E      A    B     A    --   E     --                             45    E      E      A    E     E    A    E     --                             46    A      E      A    A     E    --   C     --                             47    A      C      E    E     E    --   C     --                             48    A      C      A    A     E    A    A     --                             49    E      B      E    C     E    --   B     --                             50    A      B      A    B     E    --   A     --                             51    B      A      A    B     B    --   B     --                             52    A      A      A    B     E    A    A     --                             53    E      E      A    E     E    E    C     --                             54    E      E      A    E     E    --   E     --                             55    E      E      A    E     E    --   E     --                             56    A      E      A    E     E    --   E     --                             57    E      C      A    E     E    --   E     --                             58    A      A      E    E     E    C    E     --                             59    A      E      A    E     E    B    B     --                             60    E      C      A    E     E    B    E     --                             61    E      C      A    E     E    --   E     --                             62    A      C      A    E     C    --   C     --                             63    E      B      E    C     --   --   C     --                             64    A      E      A    E     E    --   C     --                             65    A      E      A    E     A    B    E     --                             66    B      C      A    A     A    A    --    C                              67    A      D      A    A     B    A    --    A                              68    A      E      B    A     B    E    --    C                              69    A      A      A    B     A    A    --    A                              70    A      E      E    B     B    B    --    E                              71    A      E      A    A     B    A    --    A                              72    E      B      A    E     E    B    --    A                              73    A      B      B    E     B    B    --    A                              74    A      A      A    A     A    E    --    A                              75    A      A      A    A     A    A    --    B                              76    E      E      A    B     B    B    --    E                              77    E      E      A    C     E    --   E     --                             78    A      A      A    E     B    B    --    A                              79    E      B      A    B          B    --    A                              80    A      E      A    B     C    B    --    A                              81    E      E      A    E     E    E    --    E                              82    A      C      A    A     C    E    --    E                              83    A      C      A    B     B    E    --    B                              84    A      E      A    E     E    E    --    B                              85    E      C      A    E     E    A    --    A                              86    A      C      A    E     E    B    --    A                              87    A      C      E    E     E    B    --    A                              88    E      E      A    E     E    B    --    A                              89    E      C      A    B     B    B    --    A                              90    E      B      A    B     B    B    --    A                              91    A      B      A    B     B    B    --    A                              92    E      E      A    E     B    B    --    E                              93    A      E      A    E     B    B    --    A                              94    A      E      A    E     E    --   --    A                              95    E      E      A    E     E    --   --    A                              96    E      E      E    E     E    E    --    E                              97    E      E      E    E     E    B    --    E                              98    E      E      E    E     E    B    --    E                              99    A      E      A    E     --   E    --    A                              100   E      E      E    E     B    B    --    E                              101   E      E      A    C     E    A    A     --                             102   E      E      A    C     E    A    A     --                             103   E      A      A    B     B    --   E     --                             104   E      E      B    B     E    A    A     --                             ______________________________________                                    

The aralkylimidazoles and their metal salt complexes of this inventionare useful as agricultural fungicides and as such can be applied tovarious loci such as the seed, the soil or the foliage. For suchpurposes these compounds can be used in the technical or pure form asprepared, as solutions or as formulations. The compounds are usuallytaken up in a carrier or are formulated so as to render them suitablefor subsequent dissemination as fungicides. For example, thesearalkylimidazoles or their metal salt complexes can be formulated aswettable powders, emulsifiable concentrates, dusts, granularformulations, aerosols, or flowable emulsion concentrates. In suchformulations, the compounds are extended with a liquid or solid carrierand, when desired, suitable surfactants are incorporated.

It is usually desirable, particularly in the case of foliar sprayformulations, to include adjuvants, such as wetting agents, spreadingagents, dispersing agents, stickers, adhesives and the like inaccordance with agricultural practices. Such adjuvants commonly used inthe art can be found in the John W. McCutcheon, Inc., publication"Detergents and Emulsifiers Annual."

In general, the compounds of this invention can be dissolved in certainsolvents such as acetone, methanol, ethanol, dimethylformamide, pyridineor dimethyl sulfoxide and such solutions extended with water. Theconcentration of the solution can vary from 1% to 90% with a preferredrange being 5 to 50%.

For the preparation of emulsifiable concentrates, the compound can bedissolved in suitable organic solvents, or a mixture of solvents,together with an emulsifying agent which permits dispersion of thefungicide in water. The concentration of the active ingredient inemulsifiable concentrates is usually 10% to 90% and in flowable emulsionconcentrates, this can be as high as 75%.

Wettable powders suitable for spraying, can be prepared by admixing thecompound with a finely divided solid, such as clays, inorganic silicatesand carbonates, and silicas and incorporating wetting agents, stickingagents, and/or dispersing agents in such mixtures. The concentration ofactive ingredients in such formulations is usually in the range of 20%to 98%, preferably 40% to 75%. A typical wettable powder is made byblending 50 parts of 1-[β-(2,4-dichlorophenyl)hexyl]imidazole, 45 partsof a synthetic precipitated hydrated silicon dioxide sold under thetrademark Hi-Sil®, and 5 parts of sodium lignosulfonate (Marasperse®N-22). In another preparation a kaolin type (Barden) clay is used inplace of the Hi-Sil in the above wettable powder, and in another suchpreparation 25% of the Hi-Sil is replaced with a synthetic sodium silicoaluminate sold under the trademark Zeolex® 7.

Dusts are prepared by mixing the aralkylimidazole or its metal saltcomplex with finely divided inert solids which can be organic orinorganic in nature. Materials useful for this purpose include botanicalflours, silicas, silicates, carbonates and clays. One convenient methodof preparing a dust is to dilute a wettable powder with a finely dividedcarrier. Dust concentrates containing 20% to 80% of the activeingredient are commonly made and are subsequently diluted to 1% to 10%use concentration.

The aralkylimidazoles or their metal salt complex can be applied asfungicidal sprays by methods commonly employed, such as conventionalhigh-gallonage hydraulic sprays, low-gallonage sprays, air-blast spray,aerial sprays and dusts. The dilution and rate of application willdepend upon the type of equipment employed, the method of applicationand diseases to be controlled, but the preferred effective amount isusually about 0.1 lb. to 50 lbs. per acre of the active ingredient.

As a seed protectant, the amount of toxicant coated on the seed isusually at a dosage rate of about 0.1 to 20 ounces per hundred pounds ofseed. As a soil fungicide the chemical can be incorporated in the soilor applied to the surface usually at a rate of 0.1 to 50 lbs. per acre.As a foliar fungicide, the toxicant is usually applied to growing plantsat a rate of 0.25 to 10 lbs. per acre.

Fungicides which can be combined with the fungicides of this inventionincludes:

(a) dithiocarbamates and derivatives such as: ferricdimethyldithiocarbamate (ferbam), zinc dimethyldithiocarbamate (ziram),manganese ethylenebisdithiocarbamate (maneb) and its coordinationproduct with zinc ion (mancozeb), zinc ethylenebisdithiocarbamate(zineb), zinc propylenebisdithiocarbamate (propineb), sodiummethyldithiocarbamate (metham), tetramethylthiruam disulfide (thiram),and 3,5-dimethyl-1,3,5-2H-tetrahydrothiadiazine-2-thione (dazomet);

(b) nitrophenol derivatives such as:

dinitro-(1-methylheptyl) phenyl crotonate (dinocap),

2-sec-butyl-4,6-dinitrophenyl 3,3-dimethyl acrylate (binapacryl), and

2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

(c) heterocyclic structures such as:

N-trichloromethylthiotetrahydro-phthalimide (captan),

N-trichloromethylthiopthalimide (folpet),

2-heptadecyl-2-imidazoline acetate (glyodin),

2-octylisothiazolone-3,

2,4-dichloro-6-(o-chloroanilino)-s-triazine,

diethyl phthalimidophosphorothioate,

4-butyl-1,2,4-triazole,

5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,

5-ethoxy-3-trichloromethyl-1,2,4-thiadizole,

2,3-dicyano-1,4-dithiaanthraquinone (dithianon),

2,thio-1,3-dithio-[4,5-b]quinoxaline (thioquinox),

methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate (benomyl),

2-(4-thiazolyl) benzimidazole (thiabendazole),

4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,

pyridine-2-thiol-1-oxide,

8-hydroxyquinoline sulfate,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,

α-(phenyl)-α-(2,4-dichlorophenyl)-5-pyrimidinylmethanol (triarimol),

cis-N-[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboximide,

3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyl]glutarimide(cycloheximide),

dehydroacetic acid,

N-(1,1,2,2-tetrachloroethylthio)-3a,4,

7,7a-tetrahydrophthalimide (captafol),

5-butyl-2-ethylamino-4-hydroxy-6-methylpyrimidine (ethirimol),

acetate of 4-cyclododecyl-2,6-dimethylmorpholine (dodemorph), and

6-methyl-2-oxo-1,3-dithiolo[4,5-b]-quinoxaline (quinomethionate).

(d) miscellaneous halogenated fungicides such as:

tetrachloro-p-benzoquinone (chloranil),

2,3-dichloro-1,4-naphthoquinone (dichlone),

1,4-dichloro-2,5-dimethoxybenzene (chloroneb),

3,5,6-trichloro-o-anisic acid (tricamba),

2,4,5,6-tetrachloroisophthalonitrile (TCPN),

2,6-dichloro-4-nitroaniline (dicloran),

2-chloro-1-nitropropane,

polychloronitrobenzenes such as:

pentachloronitrobenzene (PCNB) and

tetrafluorodichloroacetone;

(e) fungicidal antibiotics such as:

griseofulvin,

kasugamycin and

streptomycin;

(f) copper-based fungicides such as:

cuprous oxide,

basic cupric chloride,

basic copper carbonate,

copper naphthenate, and

Bordeaux mixture; and

(g) miscellaneous fungicides such as:

diphenyl,

dodecylguanidine acetate (dodine),

phenylmercuric acetate,

N-ethylmercuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7,-hexachlorophthalimide,

phenylmercuric monoethanol ammonium lactate,

p-dimethylaminobenzenediazo sodium sulfonate,

methyl isothiocyanate,

1-thiocyano-2,4-dinitrobenzene,

1-phenylthiosemicarbazide,

nickel-containing compounds,

calcium cyanamide,

lime sulfur,

sulfur, and

1,2-bis(3-methoxycarbonyl-2-thioureido)benzene (thiophanate-methyl).

The compounds and metal salt complexes of this invention can beadvantageously employed in various ways. Since the metal salt complexespossess inherent systemicity and broad spectrum fungicidal activity,they can be employed in the storage of cereal grain. These complexes canalso be employed as fungicides in turf and fruit orchard applications.Other applications of the metal salt complexes of this invention willsuggest themselves to those skilled in the art of agriculture andhorticulture.

We claim:
 1. A chemical compound selected from the group consisting ofan imidazole derivative having the formula ##STR50## and the active acidaddition salts thereof wherein Ar is a member selected from the groupconsisting of phenyl, mono-, di- and trihalophenyl, methylphenyl,ethylphenyl, methoxyphenyl, ethoxyphenyl, nitrophenyl andtrihalomethylphenyl, and R is a member selected from the groupconsisting of (C₁ -C₁₀) alkyl, cycloalkyl, alkenyl, cycloalkenyl andaralkyl, said aryl being a member selected from the group consisting ofphenyl, mono-, di- and trihalophenyl, methylphenyl, ethylphenyl,methoxyphenyl, ethoxyphenyl, nitrophenyl and trihalomethylphenyl,provided that when Ar is unsubstituted phenyl then R is (C₄ -C₁₀) alkyl,cycloalkyl, alkenyl, cycloalkenyl and arylalkyl, said aryl being amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl,
 2. A chemical compound selectedfrom the group consisting of an imidazole derivative having the formula##STR51## and the active acid addition salts thereof wherein Ar is amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl, and R is a member selected from thegroup consisting of alkenyl, cycloalkenyl and aralkyl, said aryl being amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl.
 3. A chemical compound selectedfrom the group consisting of an imidazole having the formula ##STR52##and the active acid addition salts thereof wherein Ar is a memberselected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl, and R is a member selected from thegroup consisting of (C₁ -C₁₀) alkyl and cycloalkyl provided that when Aris unsubstituted phenyl then R is (C₄ -C₁₀) alkyl or cycloalkyl.
 4. Achemical compound selected from the group consisting of1-[2-(2,4-dichlorophenyl)hexyl]-1H-imidazole and the active acidaddition salts thereof.
 5. A chemical compound selected from the groupconsisting of 1-[2-(2,4-dichlorophenyl)decyl]-1H-imidazole and theactive acid addition salts thereof.
 6. A chemical compound selected fromthe group consisting of1-[2-(2,4-dichlorophenyl)-4-methylpentyl]-1H-imidazole and the activeacid addition salts thereof.
 7. A chemical compound selected from thegroup consisting of an imidazole derivative having the formula ##STR53##and the active acid addition salts thereof wherein Ar is a memberselected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl, and R is a member selected from thegroup consisting of (C₁ -C₁₀) alkyl, (C₃ -C₇) cycloalkyl, (C₂ -C₁₂)alkenyl, (C₅ -C₇) cycloalkenyl and (C₇ -C₉) arylalkyl, said aryl being amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl.
 8. A chemical compound according toclaim 7 wherein R is (C₄ -C₁₀) alkyl, (C₃ -C₇) cycloalkyl, (C₂ -C₁₂)alkenyl, (C₅ -C₇) cycloalkenyl and (C₇ -C₉) arylalkyl, said aryl being amember selected from the group consisting of phenyl, mono-, di-, andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl when Ar is unsubstituted phenyl. 9.A chemical compound according to claim 7 wherein R is a member selectedfrom the group consisting of (C₁ -C₁₀) alkyl and (C₃ -C₇) cycloalkylprovided that when Ar is unsubstituted phenyl then R is (C₄ -C₁₀) alkylor (C₃ -C₇) cycloalkyl.
 10. A method for controlling phytopathogenicfungi which comprises applying to a plant, to plant seeds or to theplant habitat an effective amount of a compound of the formula:##STR54## and the active acid addition salts thereof wherein Ar is amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl, and R is a member selected from thegroup consisting of (C₁ -C₁₀) alkyl, (C₃ -C₇) cycloalkyl, (C₂ -C₁₂)alkenyl, (C₅ -C₇) cycloalkenyl and (C₇ -C₉) aralkyl, said aryl being amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl.
 11. A method according to claim 10wherein the compound is applied to the plant or plant habitat at a rateof 0.1 to 50 lbs. per acre.
 12. A method according to claim 10 whereinthe compound is applied to the plant seeds at a rate of 0.1 to 20 ouncesper hundred pounds of seed.
 13. A fungicidal composition for controllingphytopathogenic fungi which comprises an agronomically acceptablecarrier and, as the active ingredient, a compound of the formula:##STR55## and the active acid addition salts thereof wherein Ar is amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl, and R is a member selected from thegroup consisting of (C₁ -C₁₀) alkyl, (C₃ -C₇) cycloalkyl, (C₂ -C₁₂)alkenyl, (C₅ -C₇) cycloalkenyl and (C₇ -C₉) aralkyl, said aryl being amember selected from the group consisting of phenyl, mono-, di- andtrihalophenyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,nitrophenyl and trihalomethylphenyl.